Product for dyeing keratinous material, containing aminosilicone, a chromophoric compound and organic carbonic acid ester

ABSTRACT

An agent for dyeing keratinous material, in particular human hair, is disclosed. The agent is a colorant composition comprising at least one amino-functionalized silicone polymer, at least one color-imparting compound, and at least one organic carbonic acid ester. A process (method) for dyeing keratinous material with the agent is also disclosed. The process includes applying a colorant comprising the agent to the keratinous material, exposing the keratinous material to the agent for an exposure time sufficient for the color-imparting compound to act on the keratinous material, and rinsing out the keratinous material with water.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a U.S. National-Stage entry under 35 U.S.C. § 371based on International Application No. PCT/EP2020/069765, filed Jul. 13,2020, which was published under PCT Article 21(2) and which claimspriority to German Application No. 102019214462.4, filed Sep. 23, 2019,which are all hereby incorporated in their entirety by reference.

TECHNICAL FIELD

The subject of the present application is an agent for coloringkeratinous material, in particular human hair, which comprises at leastone amino-functionalized silicone polymer (a1), at least one coloringcompound (a2), and at least one organic carbonic acid ester (a3).

A second object of this application is a method for dyeing keratinousmaterial, in particular human hair, wherein an agent of the first objectof the present disclosure is applied to the keratinous material, allowedto act and then washed out again with water.

BACKGROUND

Changing the shape and color of keratinous material, especially humanhair, is a key area of modern cosmetics. To change the hair color, theexpert knows various coloring systems depending on the coloringrequirements. Oxidation dyes are usually used for permanent, intensivedyeings with good fastness properties and good grey coverage. Suchcolorants contain oxidation dye precursors, so-called developercomponents and coupler components, which, under the influence ofoxidizing agents such as hydrogen peroxide, form the actual dyes amongthemselves. Oxidation dyes are exemplified by very long-lasting dyeingresults.

When direct dyes are used, ready-made dyes diffuse from the colorantinto the hair fiber. Compared to oxidative hair dyeing, the dyeingsobtained with direct dyes have a shorter shelf life and quicker washability. Dyes with direct dyes usually remain on the hair for a periodof between 5 and 20 washes.

The use of color pigments is known for short-term color changes on thehair and/or skin. Color pigments are understood to be insoluble,coloring substances. These are present undissolved in the dyeformulation in the form of small particles and are only deposited fromthe outside on the hair fibers and/or the skin surface. Therefore, theycan usually be removed again without residue by a few washes withdetergents comprising surfactants. Various products of this type areavailable on the market under the name hair mascara.

If the user wants particularly long-lasting dyeings, the use ofoxidative dyes has so far been his only option. However, despitenumerous optimization attempts, an unpleasant ammonia or amine odorcannot be completely avoided in oxidative hair dyeing. The hair damagestill associated with the use of oxidative dyes also has a negativeeffect on the user's hair. A continuing challenge is therefore thesearch for alternative, high-performance dyeing processes. Inparticular, the color intensities and wash fastnesses of dyes based onthe use of pigments still need to be improved.

It was the task of the present disclosure to provide a dyeing systemwhich has color intensities comparable to oxidative dyeing whereverpossible. However, the oxidation dye precursors normally used for thispurpose should not be used. A technology was sought that would make itpossible to fix the colorant compounds known from the prior art (such aspigments in particular) to the hair in an extremely durable manner. Whenusing the agents in a dyeing process, particularly intensive dyeingresults with good fastness properties should be achieved. In addition,the agents should also have improved gray coverage.

Surprisingly, it has now been found that the problem can be excellentlysolved if keratinous materials, in particular hair, are colored with anagent comprising at least one amino-functionalized silicone polymer(a1), at least one coloring compound (a2), and at least one organiccarbonic acid ester (a3).

BRIEF SUMMARY

An agent for dyeing keratinous material, in particular human hair, isprovided. The agent is a colorant composition comprising (a1) at leastone amino-functionalized silicone polymer, (a2) at least onecolor-imparting compound, and (a3) at least one organic carbonic acidester.

A process (method) for dyeing keratinous material with the agent is alsoprovided. The process includes (1) applying a colorant to the keratinousmaterial, the colorant comprising the agent for dyeing keratinousmaterial. The process also includes (2) exposing the keratinous materialto the agent for an exposure time sufficient for the agent to act on thekeratinous material. The process also includes (3) rinsing out thekeratinous material with water to remove the colorant therefrom.

DETAILED DESCRIPTION

The following detailed description is merely exemplary in nature and isnot intended to limit the disclosure or the application and uses of thesubject matter as described herein. Furthermore, there is no intentionto be bound by any theory presented in the preceding background or thefollowing detailed description.

A first object of the present disclosure is an agent for coloringkeratinous material, in particular human hair, comprising.

-   (a1) at least one amino-functionalized silicone polymer, and-   (a2) at least one color-imparting compound, and-   (a3) at least one organic carbonic acid ester.

In the course of the work carried out on the present disclosure, it hasbeen surprisingly shown that the use of an organic carbonic acid ester(a3) in an agent comprising an amino silicone (a1) as well as a coloringcompound (a2) leads to an improvement in color intensity when this agentis applied in a dyeing process on the keratinous material, in particularon human hair. These positive effects were observed when the colorantcompound (a2) was a pigment.

Keratinic Material

Keratinic (keratinous) material includes hair, skin, nails (such asfingernails and/or toenails). Wool, furs and feathers also fall underthe definition of keratinous material. Preferably, keratinous materialis understood to be human hair, human skin and human nails, especiallyfingernails and toenails. Keratinous material is understood to be humanhair.

Coloring Agent

The term “coloring agent” is used in the context of the presentdisclosure for a coloring of the keratin material, of the hair, causedusing coloring compounds, in particular pigments. In this coloringprocess, the pigments are deposited as coloring compounds in aparticularly homogeneous, uniform and smooth film on the surface of thekeratin material.

Amino-Functionalized Silicone Polymers (a1)

As the first ingredient (a1) essential to the present disclosure, theagent comprises at least one amino-functionalized silicone polymer. Theamino-functionalized silicone polymer may alternatively be referred toas amino silicone or amodimethicone.

Silicone polymers are macromolecules with a molecular weight of at leastabout 500 g/mol, preferably at least about 1000 g/mol, more preferablyat least about 2500 g/mol, particularly preferably at least about 5000g/mol, which comprise repeating organic units.

The maximum molecular weight of the silicone polymer depends on thedegree of polymerization (number of polymerized monomers) and the batchsize and is partly determined by the polymerization method. For thepurposes of the present disclosure, it is preferred if the maximummolecular weight of the silicone polymer is not more than about 10⁷g/mol, preferably not more than about 10⁶ g/mol, and particularlypreferably not more than about 10⁵ g/mol.

The silicone polymers comprise many Si—O repeating units, and the Siatoms may carry organic radicals such as alkyl groups or substitutedalkyl groups. Alternatively, a silicone polymer is therefore alsoreferred to as polydimethylsiloxane.

Corresponding to the high molecular weight of silicone polymers, theseare based on more than 10 Si—O repeat units, preferably more than 50Si—O repeat units, and more preferably more than 100 Si—O repeat units,most preferably more than 500 Si—O repeat units.

An amino-functionalized silicone polymer is understood to be afunctionalized silicone that carries at least one structural unit withan amino group. Preferably, the amino-functionalized silicone polymercarries multiple structural units, each having at least one amino group.An amino group is understood to mean a primary amino group, a secondaryamino group and a tertiary amino group. All these amino groups can beprotonated in the acidic environment and are then present in theircationic form.

In principle, beneficial effects could be obtained withamino-functionalized silicone polymers (a1) if they carry at least oneprimary, at least one secondary and/or at least one tertiary aminogroup. However, dyeings with the best wash fastness were observed whenan amino-functionalized silicone polymer (a1) comprising at least onesecondary amino group was used in the agent.

In a very particularly preferred embodiment, an agent as contemplatedherein is wherein it comprises at least one amino-functionalizedsilicone polymer (a1) having at least one secondary amino group.

The secondary amino group(s) may be located at various positions on theamino-functionalized silicone polymer. Particularly beneficial effectswere found when an amino-functionalized silicone polymer (a1) was usedthat has at least one, preferably several, structural units of theformula (Si amino).

In the structural units of the formula (Si-Amino), the abbreviationsALK1 and ALK2 independently represent a linear or branched, divalentC₁-C₂₀ alkylene group.

In another very particularly preferred embodiment, an agent ascontemplated herein comprises at least one amino-functionalized siliconepolymer (a1) comprising at least one structural unit of the formula (Siamino),

where ALK1 and ALK2 independently represent a linear or branched C₁-C₂₀divalent alkylene group.

The positions marked with an asterisk (*) indicate the bond to furtherstructural units of the silicone polymer. For example, the silicon atomadjacent to the star may be bonded to another oxygen atom, and theoxygen atom adjacent to the star may be bonded to another silicon atomor even to a C₁-C₆ alkyl group.

A bivalent C₁-C₂₀ alkylene group can alternatively be referred to as adivalent or divalent C₁-C₂₀ alkylene group, by which is meant that eachALK1 or AK2 grouping can form two bonds.

In the case of ALK1, one bond occurs from the silicon atom to the ALK1grouping, and the second bond is between ALK1 and the secondary aminogroup.

In the case of ALK2, one bond is from the secondary amino group to theALK2 grouping, and the second bond is between ALK2 and the primary aminogroup.

Examples of a linear bivalent C₁-C₂₀ alkylene group include themethylene group (—CH₂—), the ethylene group (—CH₂—CH₂—), the propylenegroup (—CH₂—CH₂—CH₂—), and the butylene group (—CH₂—CH₂—CH₂—CH₂—). Thepropylene group (—CH₂—CH₂—CH₂—) is particularly preferred. From a chainlength of 3 C atoms, bivalent alkylene groups can also be branched.Examples of branched divalent, bivalent C₃-C₂₀ alkylene groups are(—CH₂—CH(CH₃)—) and (—CH₂—CH(CH₃)—CH₂—).

In another particularly preferred embodiment, the structural units ofthe formula (Si amino) represent repeat units in theamino-functionalized silicone polymer (a1), so that the silicone polymercomprises multiple structural units of the formula (Si amino).

Particularly well-suited amino-functionalized silicone polymers (a1)with at least one secondary amino group are listed below.

Dyeings with the best wash fastnesses could be obtained when the agentas contemplated herein comprises at least one amino-functionalizedsilicone polymer (a1) comprising structural units of the formula (Si-I)and of the formula (Si-II)

In a further explicitly quite particularly preferred embodiment, anagent as contemplated herein comprises at least one amino-functionalizedsilicone polymer (a1) comprising structural units of the formula (Si-I)and of the formula (Si-II)

A corresponding amino functionalized silicone polymer with thestructural units (Si-I) and (Si-II) is, for example, the commercialproduct DC 2-8566 or Dowsil 2-8566 Amino Fluid, which is commerciallydistributed by the Dow Chemical Company and bears the designation“Siloxanes and Silicones, 3-[(2-aminoethyl)amino]-2-methylpropyl Me,Di-Me-Siloxane” and the CAS number 106842-44-8.

In another preferred embodiment, an agent as contemplated hereincomprises at least one amino-functional silicone polymer (a1) of theformula (Si-III),

where

-   -   m and n mean numbers chosen so that the sum (n+m) is in the        range 1 to 1000,    -   n is a number in the range 0 to 999 and m is a number in the        range 1 to 1000,    -   R₁, R₂ and R₃, which are the same or different, denote a hydroxy        group or a C1-4 alkoxy group, and    -   wherein at least one of R1 to R3 represents a hydroxy group.

A further agent preferred as contemplated herein comprises at leastamino-functional silicone polymer (a1) of the formula of the formula(Si-IV),

where

-   -   p and q mean numbers chosen so that the sum (p+q) is in the        range 1 to 1000,    -   p is a number in the range 0 to 999 and q is a number in the        range 1 to 1000, and    -   R1 and R2, which are different, denote a hydroxy group or a C1-4        alkoxy group, at least one of R1 to R2 denoting a hydroxy group.

The silicones of the formulas (Si-III) and (Si-IV) differ in thegrouping at the Si atom, which carries the nitrogen-comprising group: Informula (Si-III), R2 represents a hydroxy group or a C1-4 alkoxy group,while the radical in formula (Si-IV) is a methyl group. The individualSi groupings, which are marked with the indices m and n or p and q, donot have to be present as blocks; rather, the individual units can alsobe present in a statistically distributed manner, i.e. in the formulas(Si-III) and (Si-IV), not every R1-Si(CH₃)₂ group is necessarily bondedto an —[O—Si(CH₃)₂] grouping.

Agents as contemplated herein which contain at least oneamino-functional silicone polymer (a1) of the formula of the formula(Si-V) have also proved to be particularly effective with respect to thedesired effects

whereA represents a group —OH, —O—Si(CH₃)₃,—O—Si(CH₃)₂OH,—O—Si(CH₃)₂OCH₃,D represents a group —H, —Si(CH₃)₃,—Si(CH₃)₂OH, —Si(CH₃)₂OCH₃,b, n and c stand for integers between 0 and 1000,with the specifications

-   -   n>0 and b+c>0    -   at least one of the conditions A=—OH or D=—H is fulfilled.

In the above formula (Si-V), the individual siloxane units arestatistically distributed with the indices b, c and n, i.e., they do notnecessarily have to be block copolymers.

The agent may further comprise one or more differentamino-functionalized silicone polymers represented by the formula(Si-VI):

M(R_(a)Q_(b)SiO_((4-a-b)/2)x)(R_(c)SiO_((4-c)/2)y)M  (Si-VI),

in which formula above R is a hydrocarbon or a hydrocarbon radicalhaving from 1 to about 6 carbon atoms, Q is a polar radical of thegeneral formula —R¹HZ wherein R¹ is a divalent linking group bonded tohydrogen and the radical Z composed of carbon and hydrogen atoms,carbon, hydrogen and oxygen atoms, or carbon, hydrogen and nitrogenatoms, and Z is an organic amino functional radical comprising at leastone amino functional group; “a” takes values ranging from about 0 toabout 2, “b” takes values ranging from about 1 to about 3, “a”+“b” isless than or equal to 3, and “c” is a number ranging from about 1 toabout 3, and x is a number ranging from 1 to about 2,000, preferablyfrom about 3 to about 50 and most preferably from about 3 to about 25,and y is a number in the range of from about 20 to about 10,000,preferably from about 125 to about 10,000 and most preferably from about150 to about 1,000, and M is a suitable silicone end group as known inthe prior art, preferably trimethylsiloxy. Non-limiting examples ofradicals represented by R include alkyl radicals, such as methyl, ethyl,propyl, isopropyl, isopropyl, butyl, isobutyl, amyl, isoamyl, hexyl,isohexyl and the like; alkenyl radicals, such as vinyl, halovinyl,alkylvinyl, allyl, haloallyl, alkylallyl; cycloalkyl radicals, such ascyclobutyl, cyclopentyl, cyclohexyl and the like; phenyl radicals,benzyl radicals, halohydrocarbon radicals, such as 3-chloropropyl,4-bromobutyl, 3,3,3-trifluoropropyl, chlorocyclohexyl, bromophenyl,chlorophenyl and the like, and sulfur-comprising radicals, such asmercaptoethyl, mercaptopropyl, mercaptohexyl, mercaptophenyl and thelike; preferably R is an alkyl radical comprising from 1 to about 6carbon atoms, and most preferably R is methyl. Examples of R¹ includemethylene, ethylene, propylene, hexamethylene, decamethylene,—CH₂CH(CH₃)CH₂—, phenylene, naphthylene,—CH₂CH₂SCH₂CH₂—, —CH₂CH₂OCH₂—,—OCH₂CH₂—, —OCH₂CH₂CH₂—, —CH₂CH(CH₃)C(O)OCH₂—, —(CH₂)₃CC(O)OCH₂CH₂—,—C₆H₄C₆H₄—, —C₆H₄CH₂C₆H₄; and —(CH₂)₃C(O)SCH₂CH₂—.

Z is an organic amino functional radical comprising at least one aminofunctional group. One formula for Z is NH(CH₂)_(z)NH₂, where z is 1 ormore. Another formula for Z is —NH(CH₂)_(z)(CH 2)_(zz)NH, wherein both zand zz are independently 1 or more, this structure comprising diaminoring structures, such as piperazinyl. Z is most preferably an—NHCH₂CH₂NH₂ radical. Another formula for Z is —N(CH₂)_(z)(CH₂)_(zz)NX₂or —NX₂, wherein each X of X₂ is independently selected from the groupof hydrogen and alkyl groups having 1 to 12 carbon atoms, and zz is 0.

Q is most preferably a polar, amine-functional radical of the formula—CH₂CH₂CH₂NHCH₂CH₂NH 2. In the formulas, “a” takes values ranging fromabout 0 to about 2, “b” takes values ranging from about 2 to about 3,“a”+“b” is less than or equal to 3, and “c” is a number ranging fromabout 1 to about 3. The molar ratio of R_(a)Q_(b)SiO_((4-a-b>/2) unitsto R_(c)SiO_((4-c)/2) units is in the range of about 1:2 to 1:65,preferably from about 1:5 to about 1:65 and most preferably by about1:15 to about 1:20. If one or more silicones of the above formula areused, then the various variable substituents in the above formula may bedifferent for the various silicone components present in the siliconemixture.

In a particularly preferred embodiment, an agent as contemplated hereincomprises at least one amino-functional silicone polymer of the formula(Si-VII)

R′_(a)G_(3-a)-Si(OSiG₂)_(n)—(OSiG_(b)R′_(2-b))_(m)—O-SiG_(3-a)-R′_(a)  (Si-VII),

wherein:

-   -   G is -H, a phenyl group, —OH, —O—CH₃, —CH₃, —O—CH₂CH₃, —CH₂CH₃,        —O—CH₂CH₂CH₃,—CH₂CH₂CH₃, —O—CH(CH₃)₂, —CH(CH₃)₂,        —O—CH₂CH₂CH₂CH₃, —CH₂CH₂CH₂CH₃, —O—CH₂CH(CH₃)₂, —CH₂CH(CH₃)₂,        —O—CH(CH₃)CH₂CH₃, —CH(CH₃)CH₂CH₃, or —O—C(CH₃)₃, —C(CH₃)₃;    -   a stands for a number between 0 and 3, especially 0;    -   b stands for a number between 0 and 1, especially 1;    -   m and n are numbers whose sum (m+n) is between 1 and 2000,        preferably between 50 and 150, where n preferably assumes values        from 0 to 1999 and from 49 to 149 and m preferably assumes        values from 1 to 2000, from 1 to 10;    -   R′ is a monovalent radical selected from    -   -Q-N(R″)—CH₂—CH₂—N(R″)₂    -   -Q-N(R″)₂    -   -Q-N⁺(R″)₃A⁻    -   -Q-N⁺H(R″)₂A⁻    -   -Q-N⁺H₂(R″)A⁻    -   -Q-N(R″)—CH₂—CH₂—N⁺R″H₂A⁻,    -   where each Q is a chemical bond, —CH₂—, —CH₂—CH₂—, —CH₂CH₂CH₂—,        —C(CH₃)₂—, —CH₂CH₂CH₂CH₂—, —CH₂C(CH₃)₂—, or —CH(CH₃)CH₂CH₂—,    -   R″ represents identical or different radicals selected from the        group of —H, -phenyl, -benzyl,—CH₂—CH(CH₃)Ph, the C₁₋₂₀ alkyl        radicals, preferably —CH₃, —CH₂CH₃, —CH₂CH₂CH₃, —CH(CH₃)₂,        —CH₂CH₂CH₂H₃, —CH₂CH(CH₃)₂, —CH(CH₃)CH₂CH₃, —C(CH₃)₃, and    -   A represents an anion preferably selected from chloride,        bromide, iodide or methosulfate.

In another preferred embodiment, an agent as contemplated herein isexemplified by comprising at least one amino-functional silicone polymer(a1) of the formula (Si-VIIa),

wherein m and n are numbers whose sum (m+n) is between 1 and 2000,preferably between 50 and 150, n preferably assuming values from 0 to1999 and from 49 to 149, and m preferably assuming values from 1 to2000, from 1 to 10.

According to the INCI declaration, these silicones are calledtrimethylsilylamodimethicones.

In the context of a further preferred embodiment, an agent ascontemplated herein comprises at least one amino-functional siliconepolymer (a1) of the formula (Si-VIIb)

in which R represents —OH, —O—CH₃ or a —CH₃ group and m, n1 and n2 arenumbers whose sum (m+n1+n2) is between 1 and 2000, preferably between 50and 150, the sum (nl+n2) preferably assuming values from 0 to 1999 andfrom 49 to 149 and m preferably assuming values from 1 to 2000, from 1to 10.

According to the INCI declaration, these amino-functionalized siliconepolymers are called amodimethicones.

Regardless of which amino-functional silicones are used, agents ascontemplated herein comprising an amino-functional silicone polymerwhose amine number is above 0.25 meq/g, preferably above 0.3 meq/g andabove 0.4 meq/g are preferred. The amine number represents themilliequivalents of amine per gram of the amino-functional silicone. Itcan be determined by titration and expressed in the unit mg KOH/g.

Furthermore, agents comprising a special 4-morpholinomethyl-substitutedsilicone polymer (a1) are also suitable. This amino-functionalizedsilicone polymer comprises structural units of the formulae (SI-VIII)and of the formula (Si-IX)

Corresponding 4-morpholinomethyl-substituted silicone polymers aredescribed below.

A very particularly preferred amino-functionalized silicone polymer isknown by the name of Amodimethicone/Morpholinomethyl SilsesquioxaneCopolymer is known and commercially available from Wacker in the form ofthe raw material Belsil ADM 8301 E.

As a 4-morpholinomethyl-substituted silicone, for example, a siliconecan be used which has structural units of the formulae (Si-VIII),(Si-IX) and (Si-X)

in whichR₁ is —CH₃, —OH, —OCH₃, —O—CH₂CH₃, —O—CH₂CH₂CH₃, or —O—CH(CH₃)₂;R₂ is —CH₃, —OH, or —OCH₃.

Particularly preferred compositions as contemplated herein contain atleast one 4-morpholinomethyl-substituted silicone of the formula (Si-XI)

located in theR₁ is —CH₃, —OH, —OCH₃, —O—CH₂CH₃, —O—CH₂CH₂CH₃, or —O—CH(CH₃)₂;R₂ is —CH₃, —OH, or —OCH₃.B represents a group —OH, —O—Si(CH₃)₃,—O—Si(CH₃)₂OH,—O—Si(CH₃)₂OCH₃,D represents a group —H, —Si(CH₃)₃,—Si(CH₃)₂OH, —Si(CH₃)₂OCH₃,a, b and c stand independently for integers between 0 and 1000, with thecondition a+b+c>0m and n independently of each other stand for integers between 1 and1000

-   -   with the proviso that        -   at least one of the conditions B=—OH or D=—H is fulfilled,        -   the units a, b, c, m and n are distributed statistically or            blockwise in the molecule.

Structural formula (Si-XI) is intended to illustrate that the siloxanegroups n and m do not necessarily have to be directly bonded to aterminal grouping B or D, respectively. Rather, in preferred formulas(Si-VI) a>0 or b>0 and in particularly preferred formulas (Si-VI) a>0and c>0, i.e., the terminal grouping B or D is preferably attached to adimethylsiloxy grouping. Also, in formula (Si-VI), the siloxane units a,b, c, m and n are preferably statistically distributed.

The silicones used as contemplated herein represented by formula (Si-VI)can be trimethylsilyl-terminated (D or B=—Si(CH₃)₃), but they can alsobe dimethylsilylhydroxy-terminated on two sides ordimethylsilylhydroxy-terminated and dimethylsilylmethoxy-terminated onone side. Silicones particularly preferred in the context of the presentdisclosure are selected from silicones in which:

-   B=—O—Si(CH₃)₂OH and D=—Si(CH₃)₃-   B=—O—Si(CH₃)₂OH and D=—Si(CH₃)₂OH-   B=—O—Si(CH₃)₂OH and D=—Si(CH₃)₂OCH₃-   B=—O—Si(CH₃)₃ and D=—Si(CH₃)₂OH-   B=—O—Si(CH₃)₂OCH₃ and D=—Si(CH₃)₂OH    These silicones lead to exorbitant improvements in the hair    properties of the hair treated with the agents of the present    disclosure, and to a seriously improved protection in oxidative    treatment.

It has been found to be particularly advantageous if the agent ascontemplated herein comprises the amino-functionalized siliconepolymer(s) (a1) in certain quantity ranges. Particularly satisfactoryresults were obtained when the agent included—based on the total weightof the agent—a total amount of from about 0.1 to about 8.0 wt. %,preferably about 0.2 to about 5.0 wt. %, more preferably about 0.3 toabout 3.0 wt. %, and most preferably about 0.4 to about 2.5 wt. %.

In another particularly preferred embodiment, an agent as contemplatedherein comprises—based on the total weight of the agent—one or moreamino-functionalized silicone polymers (a1) in a total amount of fromabout 0.1 to about 8.0 wt. %, preferably from about 0.2 to about 5.0 wt.%, more preferably from about 0.3 to about 3.0 wt. % and veryparticularly preferably from about 0.4 to about 2.5 wt. %.

Coloring Compounds (a2)

As a second essential component, the composition as contemplated hereincomprises at least one color-imparting compound (a2).

For the purposes of the present disclosure, colorant compounds aresubstances capable of imparting a coloration to the keratin material.Particularly well-suited colorant compounds can be selected from thegroup of pigments, direct-acting dyes, photochromic dyes andthermochromic dyes.

In a further preferred embodiment, a composition as contemplated hereincomprises at least one colorant compound (a2) from the group comprisingpigments, direct dyes, photochromic dyes and thermochromic dyes.

Pigments within the meaning of the present disclosure are coloringcompounds which have a solubility in water at 25° C. of less than 0.5g/L, preferably less than 0.1 g/L, even more preferably less than 0.05g/L. Water solubility can be determined, for example, by the methoddescribed below: 0.5 g of the pigment are weighed in a beaker. Astir-fish is added. Then one liter of distilled water is added. Thismixture is heated to 25° C. for one hour while stirring on a magneticstirrer. If undissolved components of the pigment are still visible inthe mixture after this period, the solubility of the pigment is below0.5 g/L. If the pigment-water mixture cannot be assessed visually due tothe high intensity of the finely dispersed pigment, the mixture isfiltered. If a proportion of undissolved pigments remains on the filterpaper, the solubility of the pigment is below 0.5 g/L.

Suitable color pigments can be of inorganic and/or organic origin.

In a preferred embodiment, an agent as contemplated herein comprises atleast one colorant compound (a2) from the group comprising inorganicand/or organic pigments.

Preferred color pigments are selected from synthetic or naturalinorganic pigments. Inorganic color pigments of natural origin can beproduced, for example, from chalk, ochre, umber, green earth, burntTerra di Siena or graphite. Furthermore, black pigments such as ironoxide black, colored pigments such as ultramarine or iron oxide red aswell as fluorescent or phosphorescent pigments can be used as inorganiccolor pigments.

Particularly suitable are colored metal oxides, hydroxides and oxidehydrates, mixed-phase pigments, sulfur-comprising silicates, silicates,metal sulfides, complex metal cyanides, metal sulphates, chromatesand/or molybdates. Preferred color pigments are black iron oxide (CI77499), yellow iron oxide (CI 77492), red and brown iron oxide (CI77491), manganese violet (CI 77742), ultramarine (sodium aluminum sulfosilicates, CI 77007, pigment blue 29), chromium oxide hydrate (CI77289),iron blue (ferric ferrocyanides, C₁₇₇₅₁₀) and/or carmine (cochineal).

As contemplated herein, colored pearlescent pigments are alsoparticularly preferred color pigments. These are usually mica- and/ormica-based and can be coated with one or more metal oxides. Mica belongsto the layer silicates. The most important representatives of thesesilicates are muscovite, phlogopite, paragonite, biotite, lepidolite andmargarite. To produce the pearlescent pigments in combination with metaloxides, the mica, muscovite or phlogopite, is coated with a metal oxide.

As an alternative to natural mica, synthetic mica coated with one ormore metal oxides can also be used as pearlescent pigment. Especiallypreferred pearlescent pigments are based on natural or synthetic mica(mica) and are coated with one or more of the metal oxides mentionedabove. The color of the respective pigments can be varied by varying thelayer thickness of the metal oxide(s).

In a further preferred embodiment, an agent as contemplated hereincomprises at least one colorant compound (a2) from the group ofinorganic pigments, which is preferably selected from the group ofcolored metal oxides, metal hydroxides, metal oxide hydrates, silicates,metal sulfides, complex metal cyanides, metal sulfates, bronze pigmentsand/or from colored mica- or mica-based pigments coated with at leastone metal oxide and/or a metal oxychloride.

In a further preferred embodiment, a composition as contemplated hereincomprises (a) at least one colorant compound (a2) from the group ofpigments selected from mica- or mica-based pigments which are reactedwith one or more metal oxides from the group comprising titanium dioxide(CI 77891), black iron oxide (CI 77499), yellow iron oxide (CI 77492),red and/or brown iron oxide (CI 77491, CI 77499), manganese violet (CI77742), ultramarine (sodium aluminum sulfosilicates, CI 77007, PigmentBlue 29), chromium oxide hydrate (CI 77289), chromium oxide (CI 77288)and/or iron blue (ferric ferrocyanide, CI 77510).

Examples of particularly suitable color pigments are commerciallyavailable under the trade names Rona®, Colorona®, Xirona®, Dichrona® andTimiron® from Merck, Ariabel® and Unipure® from Sensient, Prestige® fromEckart Cosmetic Colors and Sunshine® from Sunstar.

Particularly preferred color pigments with the trade name Colorona® are,for example:

Colorona Copper, Merck, MICA, CI 77491 (IRON OXIDES) Colorona PassionOrange, Merck, Mica, CI 77491 (Iron Oxides), Alumina Colorona PatinaSilver, Merck, MICA, CI 77499 (IRON OXIDES), CI 77891 (TITANIUM DIOXIDE)Colorona RY, Merck, CI 77891 (TITANIUM DIOXIDE), MICA, CI 75470(CARMINE) Colorona Oriental Beige, Merck, MICA, CI 77891 (TITANIUMDIOXIDE), CI 77491 (IRON OXIDES) Colorona Dark Blue, Merck, MICA,TITANIUM DIOXIDE, FERRIC FERROCYANIDE Colorona Chameleon, Merck, CI77491 (IRON OXIDES), MICA Colorona Aborigine Amber, Merck, MICA, CI77499 (IRON OXIDES), CI 77891 (TITANIUM DIOXIDE) Colorona BlackstarBlue, Merck, CI 77499 (IRON OXIDES), MICA Colorona Patagonian Purple,Merck, MICA, CI 77491 (IRON OXIDES), CI 77891 (TITANIUM DIOXIDE), CI77510 (FERRIC FERROCYANIDE) Colorona Red Brown, Merck, MICA, CI 77491(IRON OXIDES), CI 77891 (TITANIUM DIOXIDE) Colorona Russet, Merck, CI77491 (TITANIUM DIOXIDE), MICA, CI 77891 (IRON OXIDES) Colorona ImperialRed, Merck, MICA, TITANIUM DIOXIDE (CI 77891), D&C RED NO. 30 (CI 73360)Colorona Majestic Green, Merck, CI 77891 (TITANIUM DIOXIDE), MICA, CI77288 (CHROMIUM OXIDE GREENS) Colorona Light Blue, Merck, MICA, TITANIUMDIOXIDE (CI 77891), FERRIC FERROCYANIDE (CI 77510) Colorona Red Gold,Merck, MICA, CI 77891 (TITANIUM DIOXIDE), CI 77491 (IRON OXIDES)Colorona Gold Plus MP 25, Merck, MICA, TITANIUM DIOXIDE (CI 77891), IRONOXIDES (CI 77491) Colorona Carmine Red, Merck, MICA, TITANIUM DIOXIDE,CARMINE Colorona Blackstar Green, Merck, MICA, CI 77499 (IRON OXIDES)Colorona Bordeaux, Merck, MICA, CI 77491 (IRON OXIDES) Colorona Bronze,Merck, MICA, CI 77491 (IRON OXIDES) Colorona Bronze Fine, Merck, MICA,CI 77491 (IRON OXIDES) Colorona Fine Gold MP 20, Merck, MICA, CI 77891(TITANIUM DIOXIDE), CI 77491 (IRON OXIDES) Colorona Sienna Fine, Merck,CI 77491 (IRON OXIDES), MICA Colorona Sienna, Merck, MICA, CI 77491(IRON OXIDES)

Colorona Precious Gold, Merck, Mica, CI 77891 (Titanium dioxide),Silica, CI 77491(Iron oxides), Tin oxide

Colorona Sun Gold Sparkle MP 29, Merck, MICA, TITANIUM DIOXIDE, IRONOXIDES, MICA, CI 77891, CI 77491 (EU)

Colorona Mica Black, Merck, CI 77499 (Iron oxides), Mica, CI 77891(Titanium dioxide)Colorona Bright Gold, Merck, Mica, CI 77891 (Titanium dioxide), CI77491(Iron oxides)

Colorona Blackstar Gold, Merck, MICA, CI 77499 (IRON OXIDES)

Other particularly preferred color pigments with the trade name Xirona®are for example:

Xirona Golden Sky, Merck, Silica, CI 77891 (Titanium Dioxide), Tin OxideXirona Caribbean Blue, Merck, Mica, CI 77891 (Titanium Dioxide), Silica,Tin Oxide Xirona Kiwi Rose, Merck, Silica, CI 77891 (Titanium Dioxide),Tin Oxide Xirona Magic Mauve, Merck, Silica, CI 77891 (TitaniumDioxide), Tin Oxide.

In addition, particularly preferred color pigments with the trade nameUnipure® are for example:

Unipure Red LC 381 EM, Sensient CI 77491 (Iron Oxides), Silica UnipureBlack LC 989 EM, Sensient, CI 77499 (Iron Oxides), Silica Unipure YellowLC 182 EM, Sensient, CI 77492 (Iron Oxides), Silica

In a further embodiment, the composition as contemplated herein may alsocomprise one or more colorant compounds (a2) selected from the group oforganic pigments

The organic pigments as contemplated herein are correspondinglyinsoluble, organic dyes or color lacquers, which may be selected, forexample, from the group of nitroso, nitro-azo, xanthene, anthraquinone,isoindolinone, isoindolinone, quinacridone, perinone, perylene,diketo-pyrrolopyorrole, indigo, thioindido, dioxazine and/ortriarylmethane compounds.

Examples of particularly suitable organic pigments are carmine,quinacridone, phthalocyanine, sorghum, blue pigments with the ColorIndex numbers CI 42090, CI 69800, CI 69825, CI 73000, CI 74100, CI74160, yellow pigments with the Color Index numbers CI 11680, CI 11710,CI 15985, CI 19140, CI 20040, CI 21100, CI 21108, CI 47000, CI 47005,green pigments with the Color Index numbers CI 61565, CI 61570, CI74260, orange pigments with the Color Index numbers CI 11725, CI 15510,CI 45370, CI 71105, red pigments with the Color Index numbers CI 12085,CI 12120, CI 12370, CI 12420, CI 12490, CI 14700, CI 15525, CI 15580, CI15620, CI 15630, CI 15800, CI 15850, CI 15865, CI 15880, CI 17200, CI26100, CI 45380, CI 45410, CI 58000, CI 73360, CI 73915 and/or CI 75470.

In another particularly preferred embodiment, an agent as contemplatedherein comprises at least one colorant compound (a2) from the group oforganic pigments which is preferably selected from the group of carmine,quinacridone, phthalocyanine, sorghum, blue pigments having the colorindex numbers CI 42090, CI 69800, CI 69825, CI 73000, CI 74100, CI74160, yellow pigments having the color index numbers CI 11680, CI11710, CI 15985, CI 19140, CI 20040, CI 21100, CI 21108, CI 47000, CI47005, green pigments with Color Index numbers CI 61565, CI 61570, CI74260, orange pigments with Color Index numbers CI 11725, CI 15510, CI45370, CI 71105, red pigments with the Color Index numbers CI 12085, CI12120, CI 12370, CI 12420, CI 12490, CI 14700, CI 15525, CI 15580, CI15620, CI 15630, CI 15800, CI 15850, CI 15865, CI 15880, CI 17200, CI26100, CI 45380, CI 45410, CI 58000, CI 73360, CI 73915 and/or CI 75470.

The organic pigment can also be a color paint. As contemplated herein,the term color lacquer means particles comprising a layer of absorbeddyes, the unit of particle and dye being insoluble under the abovementioned conditions. The particles can, for example, be inorganicsubstrates, which can be aluminum, silica, calcium borosilate, calciumaluminum borosilicate or even aluminum.

For example, alizarin color varnish can be used.

Due to their excellent light and temperature resistance, the use of theabove pigments in the agent is particularly preferred. It is alsopreferred if the pigments used have a certain particle size. Ascontemplated herein, it is therefore advantageous if the at least onepigment has an average particle size D₅₀ of about 1.0 to about 50 μm,preferably about 5.0 to about 45 μm, preferably about 10 to about 40 μm,such as from about 14 to about 30 μm. The mean particle size D₅₀, forexample, can be determined using dynamic light scattering (DLS).

The colorant compounds (a2), the colorant compounds from the group ofpigments, represent the second essential of the agent as contemplatedherein and are preferably used in the agent in certain ranges ofamounts. Particularly satisfactory results were obtained when the agentincluded—based on the total weight of the agent—one or more pigments(a2) in a total amount of about 0.01 to about 10.0 wt. %, preferablyabout 0.1 to about 5.0 wt. %, further preferably about 0.2 to about 2.5wt. % and very preferably about 0.25 to about 1.5 wt. %.

In another very particularly preferred embodiment, an agent ascontemplated herein is wherein the agent comprises—based on the totalweight of the agent—one or more pigments (a2) in a total amount of fromabout 0.01 to about 10.0 wt. %, preferably from about 0.1 to about 5.0wt. %, more preferably from about 0.2 to about 2.5 wt. % and veryparticularly preferably from about 0.25 to about 1.5 wt. %.

As colorant compounds (a2), the agent as contemplated herein may alsocontain one or more direct dyes. Direct-acting dyes are dyes that drawdirectly onto the hair and do not require an oxidative process to formthe color. Direct dyes are usually nitrophenylene diamines,nitroaminophenols, azo dyes, anthraquinones, triarylmethane dyes orindophenols.

The direct dyes within the meaning of the present disclosure have asolubility in water (760 mmHg) at 25° C. of more than 0.5 g/L and aretherefore not to be regarded as pigments.

Preferably, the direct dyes within the meaning of the present disclosurehave a solubility in water (760 mmHg) at 25° C. of more than 1.0 g/L.

Direct dyes can be divided into anionic, cationic and non-ionic directdyes.

In a further embodiment, an agent as contemplated herein comprises atleast one colorant compound (a2) from the group comprising anionic,nonionic and cationic direct dyes.

Suitable cationic direct dyes include Basic Blue 7, Basic Blue 26, HCBlue 16, Basic Violet 2 and Basic Violet 14, Basic Yellow 57, Basic Red76, Basic Blue 16, Basic Blue 347 (Cationic Blue 347/Dystar), HC BlueNo. 16, Basic Blue 99, Basic Brown 16, Basic Brown 17, Basic Yellow 57,Basic Yellow 87, Basic Orange 31, Basic Red 51 Basic Red 76.

As non-ionic direct dyes, non-ionic nitro and quinone dyes and neutralazo dyes can be used. Suitable non-ionic direct dyes are those listedunder the international designations or Trade names HC Yellow 2, HCYellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, HC Orange 1, DisperseOrange 3, HC Red 1, HC Red 3, HC Red 10, HC Red 11, HC Red 13, HC RedBN, HC Blue 2, HC Blue 11, HC Blue 12, Disperse Blue 3, HC Violet 1,Disperse Violet 1, Disperse Violet 4, Disperse Black 9 known compounds,as well as 1,4-diamino-2-nitrobenzene, 2-amino-4-nitrophenol,1,4-bis-(2-hydroxyethyl)-amino-2-nitrobenzene,3-nitro-4-(2-hydroxyethyl)-aminophenol2-(2-hydroxyethyl)amino-4,6-dinitrophenol,4-[(2-hydroxyethyl)amino]-3-nitro-1-methylbenzene,1-amino-4-(2-hydroxyethyl)-amino-5-chloro-2-nitrobenzene,4-amino-3-nitrophenol, 1-(2′-ureidoethyl)amino-4-nitrobenzene,2-[(4-amino-2-nitrophenyl)amino]benzoic acid,6-nitro-1,2,3,4-tetrahydroquinoxaline, 2-hydroxy-1,4-naphthoquinone,picramic acid and its salts, 2-amino-6-chloro-4-nitrophenol,4-ethylamino-3-nitrobenzoic acid and2-chloro-6-ethylamino-4-nitrophenol.

Anionic direct dyes are also called acid dyes. Acid dyes are direct dyesthat have at least one carboxylic acid group (—COOH) and/or onesulphonic acid group (—SO₃H). Depending on the pH value, the protonatedforms (—COOH, —SO₃H) of the carboxylic acid or sulphonic acid groups arein equilibrium with their deprotonated forms (—COO⁻, —SO₃ ⁻ present).The proportion of protonated forms increases with decreasing pH. Ifdirect dyes are used in the form of their salts, the carboxylic acidgroups or sulphonic acid groups are present in deprotonated form and areneutralized with corresponding stoichiometric equivalents of cations tomaintain electro neutrality. Inventive acid dyes can also be used in theform of their sodium salts and/or their potassium salts.

The acid dyes within the meaning of the present disclosure have asolubility in water (760 mmHg) at 25° C. of more than 0.5 g/L and aretherefore not to be regarded as pigments. Preferably the acid dyeswithin the meaning of the present disclosure have a solubility in water(760 mmHg) at 25° C. of more than 1.0 g/L.

The alkaline earth salts (such as calcium salts and magnesium salts) oraluminum salts of acid dyes often have a lower solubility than thecorresponding alkali salts. If the solubility of these salts is below0.5 g/L (25° C., 760 mmHg), they do not fall under the definition of adirect dye.

An essential characteristic of acid dyes is their ability to formanionic charges, whereby the carboxylic acid or sulphonic acid groupsresponsible for this are usually linked to different chromophoricsystems. Suitable chromophoric systems can be found, for example, in thestructures of nitrophenylenediamines, nitroaminophenols, azo dyes,anthraquinone dyes, triarylmethane dyes, xanthene dyes, rhodamine dyes,oxazine dyes and/or indophenol dyes.

In a further embodiment, an agent for dyeing keratinous materialcomprises at least one anionic direct dye selected from the group ofnitrophenylenediamines, nitroaminophenols, azo dyes, anthraquinone dyes,triarylmethane dyes, xanthene dyes the rhodamine dyes, the oxazine dyesand/or the indophenol dyes, the dyes from the abovementioned group eachhaving at least one carboxylic acid group (—COOH), a sodium carboxylategroup (—COONa), a potassium carboxylate group (—COOK), a sulfonic acidgroup (—SO₃H), a sodium sulfonate group (—SO₃Na) and/or a potassiumsulfonate group (—SO₃K).

Suitable acid dyes may include, for example, one or more compoundsselected from the following group: Acid Yellow 1 (D&C Yellow 7, CitroninA, Ext. D&C Yellow No. 7, Japan Yellow 403, CI 10316, COLIPA n° B001),Acid Yellow 3 (COLIPA n°:C 54, D&C Yellow N° 10, Quinoline Yellow, E104,Food Yellow 13), Acid Yellow 9 (CI 13015), Acid Yellow 17 (CI 18965),Acid Yellow 23 (COLIPA n° C. 29, Covacap Jaune W 1100 (LCW), SicovitTartrazine 85 E 102 (BASF), Tartrazine, Food Yellow 4, Japan Yellow 4,FD&C Yellow No. 5), Acid Yellow 36 (CI 13065), Acid Yellow 121 (CI18690), Acid Orange 6 (CI 14270), Acid Orange 7 (2-Naphthol orange,Orange II, CI 15510, D&C Orange 4, COLIPA n° C.015), Acid Orange 10(C.I. 16230; Orange G sodium salt), Acid Orange 11 (CI 45370), AcidOrange 15 (CI 50120), Acid Orange 20 (CI 14600), Acid Orange 24 (BROWN1; CI 20170; KATSU201; nosodiumsalt; Brown No. 201; RESORCIN BROWN; ACIDORANGE 24; Japan Brown 201; D & C Brown No. 1), Acid Red 14 (C.I.14720),Acid Red 18 (E124, Red 18; CI 16255), Acid Red 27 (E 123, CI 16185,C-Rot 46, Real red D, FD&C Red Nr.2, Food Red 9, Naphthol red S), AcidRed 33 (Red 33, Fuchsia Red, D&C Red 33, CI 17200), Acid Red 35 (CIC.I.18065), Acid Red 51 (CI 45430, Pyrosin B, Tetraiodfluorescein, EosinJ, Iodeosin), Acid Red 52 (CI 45100, Food Red 106, Solar Rhodamine B,Acid Rhodamine B, Red n° 106 Pontacyl Brilliant Pink), Acid Red 73 (CI27290), Acid Red 87 (Eosin, CI 45380), Acid Red 92 (COLIPA n° C.53, CI45410), Acid Red 95 (CI 45425, Erythtosine, Simacid Erythrosine Y), AcidRed 184 (CI 15685), Acid Red 195, Acid Violet 43 (Jarocol Violet 43,Ext. D&C Violet n° 2, C.I. 60730, COLIPA n° C.063), Acid Violet 49 (CI42640), Acid Violet 50 (CI 50325), Acid Blue 1 (Patent Blue, CI 42045),Acid Blue 3 (Patent Blue V, CI 42051), Acid Blue 7 (CI 42080), Acid Blue104 (CI 42735), Acid Blue 9 (E 133, Patent Blue AE, Amido blue AE,Erioglaucin A, CI 42090, C.I. Food Blue 2), Acid Blue 62 (CI 62045),Acid Blue 74 (E 132, CI 73015), Acid Blue 80 (CI 61585), Acid Green 3(CI 42085, Foodgreen1), Acid Green 5 (CI 42095), Acid Green 9(C.I.42100), Acid Green 22 (C.I.42170), Acid Green 25 (CI 61570, JapanGreen 201, D&C Green No. 5), Acid Green 50 (Brilliant Acid Green BS,C.I. 44090, Acid Brilliant Green BS, E 142), Acid Black 1 (Black n° 401,Naphthalene Black 10B, Amido Black 10B, CI 20 470, COLIPA n° B15), AcidBlack 52 (CI 15711), Food Yellow 8 (CI 14270), Food Blue 5, D&C Yellow8, D&C Green 5, D&C Orange 10, D&C Orange 11, D&C Red 21, D&C Red 27,D&C Red 33, D&C Violet 2 and/or D&C Brown 1.

For example, the water solubility of anionic direct dyes can bedetermined in the following way. 0.1 g of the anionic direct dye isplaced in a beaker. A stir-fish is added. Then add 100 ml of water. Thismixture is heated to 25° C. on a magnetic stirrer while stirring. It isstirred for 60 minutes. The aqueous mixture is then visually assessed.If there are still undissolved radicals, the amount of water isincreased—for example in steps of 10 ml. Water is added until the amountof dye used is completely dissolved. If the dye-water mixture cannot beassessed visually due to the high intensity of the dye, the mixture isfiltered. If a proportion of undissolved dyes remains on the filterpaper, the solubility test is repeated with a higher quantity of water.If 0.1 g of the anionic direct dye dissolves in 100 ml water at 25° C.,the solubility of the dye is 1.0 g/L.

Acid Yellow 1 is called 8-hydroxy-5,7-dinitro-2-naphthalenesulfonic aciddisodium salt and has a solubility in water of at least 40 g/L (25° C.).Acid Yellow 3 is a mixture of the sodium salts of mono- and sisulfonicacids of 2-(2-quinolyl)-1H-indene-1,3(2H)-dione and has a watersolubility of 20 g/L (25° C.). Acid Yellow 9 is the disodium salt of8-hydroxy-5,7-dinitro-2-naphthalenesulfonic acid, its solubility inwater is above 40 g/L (25° C.). Acid Yellow 23 is the trisodium salt of4,5-dihydro-5-oxo-1-(4-sulfophenyl)-4-((4-sulfophenyl)azo)-1H-pyrazole-3-carboxylicacid and is highly soluble in water at 25° C. Acid Orange 7 is thesodium salt of 4-[(2-hydroxy-1-naphthyl)azo]benzene sulphonate. Itswater solubility is more than 7 g/L (25° C.). Acid Red 18 is thetrinatirum salt of7-hydroxy-8-[(E)-(4-sulfonato-1-naphthyl)-diazenyl)]-1,3-naphthalenedisulfonate and has a remarkably high water solubility of more than 20wt. %. Acid Red 33 is the diantrium salt of5-amino-4-hydroxy-3-(phenylazo)-naphthalene-2,7-disulphonate, itssolubility in water is 2.5 g/L (25° C.). Acid Red 92 is the disodiumsalt of3,4,5,6-tetrachloro-2-(1,4,5,8-tetrabromo-6-hydroxy-3-oxoxanthen-9-yl)benzoicacid, whose solubility in water is indicated as greater than 10 g/L (25°C.). Acid Blue 9 is the disodium salt of2-({4-[N-ethyl(3-sulfonatobenzyl]amino]phenyl}{4-[(N-ethyl(3-sulfonatobenzyl)imino]-2,5-cyclohexadien-1-ylidene}methyl)-benzenesulfonateand has a solubility in water of more than 20 wt. % (25° C.).

In a further embodiment, an agent as contemplated herein is thereforewherein it comprises at least one direct dye (a2) selected from thegroup of acid yellow 1, acid yellow 3, acid yellow 9, Acid Yellow 17,Acid Yellow 23, Acid Yellow 36, Acid Yellow 121, Acid Orange 6, AcidOrange 7, Acid Orange 10, Acid Orange 11, Acid Orange 15, Acid Orange20, Acid Orange 24, Acid Red 14, Acid Red 27, Acid Red 33, Acid Red 35,Acid Red 51, Acid Red 52, Acid Red 73, Acid Red 87, Acid Red 92, AcidRed 95, Acid Red 184, Acid Red 195, Acid Violet 43, Acid Violet 49, AcidViolet 50, Acid Blue 1, Acid Blue 3, Acid Blue 7, Acid Blue 104, AcidBlue 9, Acid Blue 62, Acid Blue 74, Acid Blue 80, Acid Green 3, AcidGreen 5, Acid Green 9, Acid Green 22, Acid Green 25, Acid Green 50, AcidBlack 1, Acid Black 52, Food Yellow 8, Food Blue 5, D&C Yellow 8, D&CGreen 5, D&C Orange 10, D&C Orange 11, D&C Red 21, D&C Red 27, D&C Red33, D&C Violet 2 and/or D&C Brown 1.

The direct-acting dye or dyes can be used in various amounts in theagents, depending on the desired color intensity. Satisfactory resultswere obtained when the agent comprises—based on the total weight of theagent—one or more direct dyes (a2) in a total amount of from about 0.01to about 10.0 wt. %, preferably from about 0.1 to about 8.0 wt. 00 morepreferably from about 0.2 to about 6.0 wt. % and most preferably fromabout 0.5 to about 4.5 wt. %.

Furthermore, the agent may also contain at least one photochromic orthermochromic dye as the coloring compound (a2).

Photochromic dyes are dyes that react to irradiation with UV light(sunlight or black light) with a reversible change in hue. In thisprocess, the UV light changes the chemical structure of the dyes andthus their absorption behavior (photochromism).

Thermochromic dyes are dyes that react to temperature changes with areversible change in hue. In this process, the change in temperaturealters the chemical structure of the dyes and thus their absorptionbehavior (Thermochromism).

The agent may contain—based on the total weight of the composition—oneor more photochromic dyes (a2) in a total amount of from about 0.01 toabout 10.0 wt. %, preferably from about 0.1 to about 8.0 wt. %, morepreferably from about 0.2 to about 6.0 wt. % and most preferably fromabout 0.5 to about 4.5 wt. %

Organic Carbonic Acid Esters (a3)

As a third essential ingredient (a3), the agents as contemplated hereincontain at least one organic carbonic acid ester.

Organic carbonic acid esters are the esters of carbonic acid, which isunstable in substance. Its general structural formula isR′—O—C(═O)—O—R″′, where R′ and R″ are either hydrogen or an organicradical, with at least one of R′ and R″ being an organic radical.

If the radicals R′ and R″ are equal, then the carbonic ester (a3) issymmetric; if R′ is not equal to R″, then the carbonic ester (a3) isasymmetric. If R′ and R″ belong to the same organic structural unit, aring-shaped carbonic acid ester is present.

If the carbonic acid function is unfunctionalized on one side, i.e., ifR′ or R″ represent hydrogen, then a carbonic acid half-ester is present.

If both R′ and R″ represent an organic radical, then a carbonic aciddiester is present.

The organic carbonic acid esters of the general formula (KSE-I) haveshown particularly good suitability for solving the task as contemplatedherein

whereR1,R2 together with the two oxygen atoms to which they are attached andtogether with the carbonyl group form a 5-membered, 6-membered or7-membered ring which may optionally be substituted with a C₁-C₁₂ alkylgroup, a hydroxy-C₁-C₆ alkyl group, a hydroxy group or a C₁-C₆ alkoxygroup, or R1 and R2 independently represent a C₁-C₁₂ alkyl group, ahydroxy-C₁-C₁₂ alkyl group or an optionally substituted aryl group.

Examples of a C₁-C₁₂ alkyl group include the methyl group, the ethylgroup, the n-propyl group, the isopropyl group, the n-butyl group, then-pentyl group, the n-hexyl group, the n-octyl group, and the n-dodecylgroup. Exemplary hydroxy-C₁-C₆ alkyl groups may include hydroxymethylgroup and 2-(hydroxyethyl group) and 3-(hydroxyrpopyl group). Examplesof a C₁-C₆ alkoxy group include the methoxy group and the ethoxy group.Suitable aryl groups include the phenyl group and the naphthyl group.

In the context of a further very particularly preferred embodiment, anagent as contemplated herein comprises

(a3) at least one organic carbonic acid ester of the general formula(KSE-I)

whereR1,R2 together with the two oxygen atoms to which they are attached andtogether with the carbonyl group form a 5-membered, 6-membered or7-membered ring which may optionally be substituted with a C₁-C₁₂ alkylgroup, a hydroxy-C₁-C₆ alkyl group, a hydroxy group or a C₁-C₆ alkoxygroup, or R1 and R2 independently represent a C₁-C₁₂ alkyl group, ahydroxy-C₁-C₁₂ alkyl group or an optionally substituted aryl group.

As contemplated herein, the use of cyclic carbonic acid esters isparticularly suitable. Very particularly preferred cyclic esters ofcarbonic acid are called 1,3-dioxolan-2-ones and can be described by thefollowing structure.

In the basic body of 1,3-dioxolan-2-ones, two H atoms are bonded in eachof the 4- and 5-positions. It is possible and preferred in the contextof the present disclosure to also use derivatives of this basicstructure, i.e., 1,3-dioxolan-2-ones substituted in the 4- or 4- and5-position. There are no limits to the structural diversity here, sothat mono-, di-, tri- and tetra-substituted 1,3-dioxolan-2-ones aresuitable for use in the context of the present disclosure.

A particularly strong increase in color intensity was observed when anagent as contemplated herein was dyed on keratinous material comprisingat least one cyclic organic carbonic acid ester (a3). Very preferably,this cyclic organic carbonic acid ester was a substance from the groupof substituted or unsubstituted 1,3-dioxolan-2-one.

In the context of a further very particularly preferred embodiment, anagent as contemplated herein is wherein

(a3) comprises at least one cyclic organic carbonic acid ester which ispreferably selected from the group of substituted or unsubstituted1,3-dioxolan-2-one.

Particularly preferred, in addition to the unsubstituted1,3-dioxolan-2-one, are the derivatives monosubstituted in the4-position of the following formula

in which R is a substituted or unsubstituted alkyl, alkenyl or alkylarylradical. Preferred radicals R are methyl, ethyl, n-propyl, iso-propyl,and hydroxymethyl and hydroxyethyl radicals.

Most preferably, R represents a methyl group, an ethyl group, ann-propyl group, an iso-propyl group, a hydroxymethyl group or ahydroxyethyl group.

In the context of a further very particularly preferred embodiment, anagent as contemplated herein is wherein

(a3) comprises at least one organic carbonic acid ester of the generalformula (KSE-II)

whereR3 represents a methyl group, an ethyl group, an n-propyl group, aniso-propyl group, a hydroxymethyl group or a hydroxyethyl group.

Particularly preferred 1,3-dioxolan-2-ones are from the group ethylenecarbonate (R ═H), propylene carbonate (R═CH₃) and glycerol carbonate(R═CH₂OH).

Ethylene carbonate is a colorless crystalline compound that melts at 39°C. and boils at 238° C. Ethylene carbonate, which is readily soluble inwater, alcohols and organic solvents, can be produced from ethyleneoxide and liquid CO₂ via large-scale syntheses.

Propylene carbonate is a water-light, easily movable liquid, with adensity of 1.2057 gcm⁻³, the melting point is −49° C., the boiling pointis 242° C. Propylene carbonate is also accessible on a large scale byreacting propylene oxide and CO₂ at 200° C. and 80 bar. Glycerolcarbonate is accessible by transesterification of ethylene carbonate ordimethyl carbonate with glycerol, yielding ethylene glycol or methanolas by-products. Another synthetic route starts from glycidol(2,3-epoxy-1-propanol), which is reacted with CO₂ under pressure in thepresence of catalysts to form glycerol carbonate.

Glycerol carbonate is a clear, easily movable liquid with a density of1.398 gcm⁻³ that boils at 125-130° C. (0.15 mbar).

Beneficial effects were also obtained when non-cyclic carbonic acidesters (a3) were used in the agent as contemplated herein.

Both carbonic acid monoesters and carbonic acid diesters are suitablefor use in the agent as contemplated herein. Agents suitable ascontemplated herein contain at least one carbonic acid monoester of theformula (KSE-III):

R4-O—C(O)—O—H  (KSE-III),

in which R4 represents a saturated or unsaturated, linear or branched,optionally substituted C₁-C₈ alkyl group, or a substituted orunsubstituted aryl group or a substituted or unsubstituted heterocycle.

In formula (KE-III), R4 is preferably a substituted or unsubstituted,straight-chain or branched alkyl, alkenyl or alkynyl radical, withhydroxy, amino, nitro, sulfonic acid groups or halogens being preferredsubstituents. Other preferred radicals R are phenyl and benzyl radicalsand further substituted representatives. Particularly preferably, Rstands for a C₁₋₆ alkyl group. Examples of C₁-C₆ alkyl groups ascontemplated herein are the groups methyl, ethyl, n-propyl, isopropyl,n-butyl, sec-butyl, iso-butyl, tert-butyl, pentyl, iso-pentyl and hexyl.

Agents suitable as contemplated herein are wherein the radical R1 informula (I) is selected from methyl, ethyl, n-propyl, iso-propyl,n-butyl, iso-butyl, tert-butyl and hydroxymethyl and hydroxyethylradicals.

The acidic H atom of the carbonic acid monoester can also be present inneutralized form, i.e., salts of carbonic acid monoesters can also beused as contemplated herein. Here, agents as contemplated herein arepreferred which contain the carbonic acid monoester carbonic acidmonoamide in completely or partially neutralized form, preferably in theform of its alkali metal, ammonium, alkaline earth metal or aluminumsalt and in the form of its sodium salt.

Carbonic acid diesters (a3) can be used as further well-suited esters ofcarbonic acid in the agent of the present disclosure. Agents preferredas contemplated herein therefore contain at least one carbonic aciddiester of the formula (KSE-IV):

R5-O—C(O)—O—R6  (KSE-IV),

in which R5 and R6 are each independently of the other a saturated orunsaturated, straight-chain, branched or cyclic, substituted orunsubstituted C1-C8 hydrocarbon radical, or a substituted orunsubstituted aryl group or a substituted or unsubstituted heterocycle.

In formula (KE-IV), R5 and R6 each independently preferably represent asubstituted or unsubstituted, straight-chain or branched alkyl, alkenylor alkynyl radical, with hydroxy, amino, nitro, sulfonic acid groups orhalogens preferably being suitable substituents. Further preferredradicals R or R′ are phenyl and benzyl radicals as well as furthersubstituted representatives. Particularly preferably, R or R′ representsa C₁₋₆ alkyl group. Examples of C₁-C₆ alkyl groups as contemplatedherein are the groups methyl, ethyl, n-propyl, isopropyl, n-butyl,sec-butyl, iso-butyl, tert-butyl, pentyl, iso-pentyl and hexyl.

Agents particularly preferred as contemplated herein are wherein theradicals R5 and R6 in formula (KE-IV) are each independently selectedfrom methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyland hydroxymethyl and hydroxyethyl radicals.

Particularly preferred organic carbonic acid esters (a3) may be selectedfrom the group of 4-methyl-1,3-dioxolane, 4-hydroxymethyl-1-3-dioxolane,di(n-octyl carbonate), di(n-hexyl carbonate), di(n-propyl carbonate),dimethyl carbonate, diethyl carbonate, and diphenyl carbonate.

In the context of a further very particularly preferred embodiment, anagent as contemplated herein is wherein:

(a3) at least one organic carbonic acid ester selected from the group of4-methyl-1,3-dioxolane, 4-hydroxymethyl-1-3-dioxolane, di(n-octylcarbonate), di(n-hexyl carbonate), di(n-propyl carbonate), dimethylcarbonate, diethyl carbonate, and diphenyl carbonate.4-Methyl-1,3-dioxolane (a3) is most preferred.

The organic carbonic acid esters, for example, can also be purchasedcommercially from common suppliers of fine chemicals, such as Aldrich orFluka.

The organic carbonic acid esters (a3) are particularly preferred incertain ranges of amounts in the agent as contemplated herein.

Particularly satisfactory results were obtained when the agentincluded—based on the total weight of the agent—one or more organiccarbonic acid esters (a3) in a total amount of from about 0.1 to about20.0 wt. %, preferably from about 0.5 to about 15.0 wt. %, morepreferably from about 1.0 to about 10.0 wt. % and most preferably fromabout 4.0 to about 8.0 wt. %.

In a further preferred embodiment, an agent as contemplated hereincomprises—based on the total weight of the agent—one or more organiccarbonic acid esters (a3) in a total amount of from about 0.1 to about20.0 wt. %, preferably from about 0.5 to about 15.0 wt. %, morepreferably from about 1.0 to about 10.0 wt. % and very preferably fromabout 4.0 to about 8.0 wt. %.

Fat Components in Agent

As a further optional ingredient, the agent as contemplated herein mayalso additionally comprise at least one fat ingredient.

It has been found that the use of at least one fat component results inthe agent being in the form of an emulsion, which has the optimumviscosity and has also been found to be beneficial in terms of improvingcolor intensity.

The fatty components are hydrophobic substances that can form emulsionsin the presence of water, forming micelle systems.

For the purposes of the present disclosure, “fatty components” meansorganic compounds with a solubility in water at room temperature (22°C.) and atmospheric pressure (760 mmHg) of less than 1 wt. %, preferablyless than 0.1 wt. %. The definition of fat constituents explicitlycovers only uncharged (i.e., non-ionic) compounds. Fat components haveat least one saturated or unsaturated alkyl group with at least 12 Catoms. The molecular weight of the fat constituents is a maximum ofabout 5000 g/mol, preferably a maximum of about 2500 g/mol andparticularly preferably a maximum of about 1000 g/mol. The fatcomponents are neither ethoxylated, nor polyoxyalkylated, norpolyglycerylated compounds.

Very preferably, the fat constituents (a4) included in the compositionare selected from the group of C₁₂-C₂₄ fatty alcohols, C₁₂-C₂₄ fattyacid triglycerides, C₁₂-C₂₄ fatty acid monoglycerides, C₁₂-C₂₄ fattyacid diglycerides and/or hydrocarbons.

In the context of a further preferred embodiment, an agent ascontemplated herein comprises one or more fat constituents from thegroup comprising the C₁₂-C₂₄ fatty alcohols, the C₁₂-C₂₄ fatty acidtriglycerides, the C₁₂-C₂₄ fatty acid monoglycerides, the C₁₂-C₂₄ fattyacid diglycerides and/or the hydrocarbons.

In this context, very particularly preferred fat constituents areunderstood to be constituents from the group of C₁₂-C₂₄ fatty alcohols,C₁₂-C₂₄ fatty acid triglycerides, C₁₂-C₂₄ fatty acid monoglycerides,C₁₂-C₂₄ fatty acid diglycerides and/or hydrocarbons. For the purposes ofthe present disclosure, only non-ionic substances are explicitlyregarded as fat components. Charged compounds such as fatty acids andtheir salts are not considered to be fat components.

The C₁₂-C₂₄ fatty alcohols can be saturated, mono- or polyunsaturated,linear or branched fatty alcohols with 12 to 24 C atoms.

Examples of preferred linear, saturated C12-C₂₄ fatty alcohols aredodecan-1-ol (dodecyl alcohol, lauryl alcohol), tetradecan-1-ol(tetradecyl alcohol, myristyl alcohol), hexadecan-1-ol (hexadecylalcohol, Cetyl alcohol, palmityl alcohol), octadecan-1-ol (octadecylalcohol, stearyl alcohol), arachyl alcohol (eicosan-1-ol), heneicosylalcohol (heneicosan-1-ol) and/or behenyl alcohol (docosan-1-ol).

Preferred linear unsaturated fatty alcohols are (9Z)-octadec-9-en-1-ol(oleyl alcohol), (9E)-octadec-9-en-1-ol (elaidyl alcohol),(9Z,12Z)-octadeca-9,12-dien-1-ol (linoleyl alcohol),(9Z,12Z,15Z)-octadeca-9,12,15-trien-1-ol (linolenoyl alcohol), gadoleylalcohol ((9Z)-eicos-9-en-1-ol), arachidone alcohol((5Z,8Z,11Z,14Z)-eicosa-5,8,11,14-tetraen-1-ol), erucyl alcohol((13Z)-docos-13-en-1-ol) and/or brassidyl alcohol ((13E)-docosen-1-ol).

The preferred representatives for branched fatty alcohols are2-octyl-dodecanol, 2-hexyl-dodecanol and/or 2-butyl-dodecanol.

In the context of a further preferred embodiment, an agent ascontemplated herein comprises at least one C₁₂-C₂₄ fatty alcohol,preferably selected from the group of.

Dodecan-1-ol (dodecyl alcohol, lauryl alcohol),Tetradecan-1-ol (tetradecyl alcohol, myristyl alcohol),Hexadecan-1-ol (hexadecyl alcohol, cetyl alcohol, palmityl alcohol),Octadecan-1-ol (octadecyl alcohol, stearyl alcohol),Arachyl alcohol (eicosan-1-ol),Heneicosyl alcohol (heneicosan-1-ol),Behenyl alcohol (docosan-1-ol),(9Z)-Octadec-9-en-1-ol (oleyl alcohol),(9E)-Octadec-9-en-1-ol (elaidyl alcohol),(9Z,12Z)-Octadeca-9,12-dien-1-ol (linoleyl alcohol),(9Z,12Z,15Z)-Octadeca-9,12,15-trien-1-ol (linolenoyl alcohol),Gadoleyl alcohol ((9Z)-Eicos-9-en-1-ol),Arachidonic alcohol ((5Z,8Z,11Z,14Z)-Eicosa-5,8,11,14-tetraen-1-ol),Erucyl alcohol ((13Z)-docos-13-en-1-ol),Brassidyl alcohol ((13E)-docosen-1-ol),

2-Octyl-dodecanol,

2-hexyl dodecanol and/or

2-Butyl-dodecanol.

It has been found to be quite preferable to use one or more C₁₂-C₂₄fatty alcohols in quite specific ranges of amounts.

It is particularly preferred if the agent comprises one or more C₁₂-C₂₄fatty alcohols in a total amount—based on the total weight of thecomposition—of from about 2.0 to about 50.0 wt. %, preferably from about3.0 to about 30.0 wt. %, more preferably from about 4.0 to about 20.0wt. %, still more preferably from about 5.0 to about 15.0 wt. %, andmost preferably from about 5.0 to about 10.0 wt. %.

Further, as a suitable fat ingredient, the agent may also contain atleast one C₁₂-C₂₄ fatty acid triglyceride that is C₁₂-C₂₄ fatty acidmonoglyceride and/or C₁₂-C₂₄ fatty acid diglyceride. For the purposes ofthe present disclosure, a C₁₂-C₂₄ fatty acid triglyceride is understoodto be the triester of the trivalent alcohol glycerol with threeequivalents of fatty acid. Both structurally identical and differentfatty acids within a triglyceride molecule can be involved in theformation of esters.

As contemplated herein, fatty acids are to be understood as saturated orunsaturated, unbranched or branched, unsubstituted or substitutedC₁₂-C₂₄ carboxylic acids. Unsaturated fatty acids can be mono- orpolyunsaturated. For an unsaturated fatty acid, its C—C double bond(s)may have the Cis or Trans configuration.

Fatty acid triglycerides are particularly suitable in which at least oneof the ester groups is formed from glycerol with a fatty acid selectedfrom dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid),hexadecanoic acid (palmitic acid), tetracosanoic acid (lignoceric acid),octadecanoic acid (stearic acid), eicosanoic acid (arachidic acid),docosanoic acid (behenic acid), petroselinic acid [(Z)-6-octadecenoicacid], palmitoleic acid [(9Z)-hexadec-9-enoic acid], oleic acid[(9Z)-octadec-9-enoic acid], elaidic acid [(9E)-octadec-9-enoic acid],erucic acid [(13Z)-docos-13-enoic acid], linoleic acid[(9Z,12Z)-octadeca-9,12-dienoic acid, linolenic acid[(9Z,12Z,15Z)-octadeca-9,12,15-trienoic acid, elaeostearic acid[(9Z,11E,13E)-octadeca-9,11,3-trienoic acid], arachidonic acid[(5Z,8Z,11Z,14Z)-icosa-5,8,11,14-tetraenoic acid], and/or nervonic acid[(15Z)-tetracos-15-enoic acid].

The fatty acid triglycerides can also be of natural origin. The fattyacid triglycerides or mixtures thereof occurring in soybean oil, peanutoil, olive oil, sunflower oil, macadamia nut oil, moringa oil, apricotkernel oil, marula oil and/or optionally hardened castor oil areparticularly suitable for use in the product as contemplated herein.

A C₁₂-C₂₄ fatty acid monoglyceride is understood to be the monoester ofthe trivalent alcohol glycerol with one equivalent of fatty acid. Eitherthe middle hydroxy group of glycerol or the terminal hydroxy group ofglycerol may be esterified with the fatty acid.

C₁₂-C₂₄ fatty acid monoglycerides are particularly suitable in which ahydroxyl group of glycerol is esterified with a fatty acid, the fattyacids being selected from dodecanoic acid (lauric acid), tetradecanoicacid (myristic acid), hexadecanoic acid (palmitic acid), tetracosanoicacid (lignoceric acid), octadecanoic acid (stearic acid), eicosanoicacid (arachidic acid), docosanoic acid (behenic acid), petroselinic acid[(Z)-6-octadecenoic acid], palmitoleic acid [(9Z)-hexadec-9-enoic acid],oleic acid [(9Z)-octadec-9-enoic acid], elaidic acid[(9E)-octadec-9-enoic acid], erucic acid [(13Z)-docos-13-enoic acid],linoleic acid [(9Z,12Z)-octadeca-9,12-dienoic acid, linolenic acid[(9Z,12Z,15Z)-octadeca-9,12,15-trienoic acid, elaeostearic acid[(9Z,11E,13E)-octadeca-9,11,3-trienoic acid], arachidonic acid[(5Z,8Z,11Z,14Z)-icosa-5,8,11,14-tetraenoic acid], or nervonic acid[(15Z)-tetracos-15-enoic acid].

A C₁₂-C₂₄ fatty acid diglyceride is the diester of the trivalent alcoholglycerol with two equivalents of fatty acid. Either the middle and oneterminal hydroxy group of glycerol may be esterified with twoequivalents of fatty acid, or both terminal hydroxy groups of glycerolare esterified with one fatty acid each. The glycerol can be esterifiedwith two structurally identical fatty acids or with two different fattyacids.

Fatty acid triglycerides are particularly suitable in which at least oneof the ester groups is formed from glycerol with a fatty acid selectedfrom dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid),hexadecanoic acid (palmitic acid), tetracosanoic acid (lignoceric acid),octadecanoic acid (stearic acid), eicosanoic acid (arachidic acid),docosanoic acid (behenic acid), petroselinic acid [(Z)-6-octadecenoicacid], palmitoleic acid [(9Z)-hexadec-9-enoic acid], oleic acid[(9Z)-octadec-9-enoic acid], elaidic acid [(9E)-octadec-9-enoic acid],erucic acid [(13Z)-docos-13-enoic acid], linoleic acid[(9Z,12Z)-octadeca-9,12-dienoic acid, linolenic acid[(9Z,12Z,15Z)-octadeca-9,12,15-trienoic acid, elaeostearic acid[(9Z,11E,13E)-octadeca-9,11,3-trienoic acid], arachidonic acid[(5Z,8Z,11Z,14Z)-icosa-5,8,11,14-tetraenoic acid], and/or nervonic acid[(15Z)-tetracos-15-enoic acid].

Particularly good results were obtained when the agent included at leastone C₁₂-C₂₄-fatty acid monoglyceride selected from the monoesters ofglycerol with one equivalent of fatty acid from the group comprisingdodecanoic acid (lauric acid), tetradecanoic acid (myristic acid),hexadecanoic acid (palmitic acid), tetracosanoic acid (lignoceric acid),octadecanoic acid (stearic acid), eicosanoic acid (arachidic acid),docosanoic acid (behenic acid), Petroselic acid [(Z)-6-octadecenoicacid], Palmitoleic acid [(9Z)-Hexadec-9-enoic acid], Oleic acid[(9Z)-Octadec-9-enoic acid], Elaidic acid [(9E)-Octadec-9-enoic acid],Erucic acid [(13Z)-Docos-13-enoic acid], Linoleic acid[(9Z,12Z)-Octadeca-9,12-dienoic acid, linolenic acid[(9Z,12Z,15Z)-octadeca-9,12,15-trienoic acid, elaeostearic acid[(9Z,11E,13E)-octadeca-9,11,3-trienoic acid], arachidonic acid[(5Z,8Z,11Z,14Z)-icosa-5,8,11,14-tetraenoic acid] and/or nervonic acid[(15Z)-tetracos-15-enoic acid].

In the context of a further embodiment, an agent as contemplated hereincomprises at least one C₁₂-C₂₄ fatty acid monoglyceride selected fromthe monoesters of glycerol with one equivalent of fatty acid from thegroup comprising dodecanoic acid, tetradecanoic acid, hexadecanoic acid,tetracosanoic acid, octadecanoic acid, eicosanoic acid and/or docosanoicacid.

It has been found preferable to use one or more C₁₂-C₂₄ fatty acidmono-, C₁₂-C₂₄-fatty acid di- and/or C₁₂-C₂₄ fatty acid triglycerides inspecific ranges of amounts in the agent.

With regard to the solution of the task as contemplated herein, it hasproved advantageous if the agent—based on the total weight of theagent—included one or more C₁₂-C₂₄ fatty acid mono-, C₁₂-C₂₄ fatty aciddi- and/or C₁₂-C₂₄ fatty acid triglycerides in a total amount of about0.1 to about 20.0 wt. %, preferably from about 0.3 to about 15.0 wt. %,more preferably from about 0.5 to about 10.0 wt. %, and most preferablyfrom about 0.8 to about 5.0 wt. %.

Furthermore, as a very particularly preferred fat constituent, theagents may also contain at least one hydrocarbon.

Hydrocarbons are compounds comprising exclusively of the atoms carbonand hydrogen with 8 to 80 C atoms. In this context, aliphatichydrocarbons such as mineral oils, liquid paraffin oils (e.g.,Paraffinum Liquidum or Paraffinum Perliquidum), isoparaffin oils,semi-solid paraffin oils, paraffin waxes, hard paraffin (ParaffinumSolidum), Vaseline and polydecenes are particularly preferred.

Liquid paraffin oils (Paraffinum Liquidum and Paraffinum Perliquidum)have proven to be particularly suitable in this context. ParaffinumLiquidum, also known as white oil, is the preferred hydrocarbon.Paraffinum Liquidum is a mixture of purified, saturated, aliphatichydrocarbons, comprising hydrocarbon chains with a C-chain distributionof 25 to 35 C-atoms.

Particularly satisfactory results were obtained when the agent includedat least one hydrocarbon selected from the group of mineral oils, liquidkerosene oils, isoparaffin oils, semisolid kerosene oils, kerosenewaxes, hard kerosene (Paraffinum solidum), petrolatum and polydecenes.

In a very particularly preferred embodiment, an agent as contemplatedherein comprises at least one fatty constituent from the group ofhydrocarbons.

Regarding the solution of the problem as contemplated herein, it provedto be quite particularly preferable if the agent included—based on thetotal weight of the composition—one or more hydrocarbons in a totalamount of from 0.5 to 20.0 wt. %, preferably from 0.7 to 10.0 wt. %,more preferably from 0.9 to 5.0 wt. % and very particularly preferablyfrom 1.0 to 4.0 wt. %.

In a very particularly preferred embodiment, an agent as contemplatedherein comprises—based on the total weight of the agent—one or morehydrocarbons in a total amount of in a total amount of from about 0.5 toabout 20.0 wt. %, preferably from about 0.7 to about 10.0 wt. %, morepreferably from about 0.9 to about 5.0 wt. % and very particularlypreferably from about 1.0 to about 4.0 wt. %.

Surfactants in the Agent

As a further optional ingredient, the agents as contemplated herein mayalso additionally comprise at least one surfactant. To further optimizethe formation of the emulsion, it has proven particularly preferable tocontinue to use at least one nonionic surfactant in the agent.

Quite preferably, therefore, the agent as contemplated hereinadditionally comprises at least one surfactant.

The term surfactants (T) refer to surface-active substances that canform adsorption layers on surfaces and interfaces or aggregate in bulkphases to form micelle colloids or lyotropic mesophases. A distinctionis made between anionic surfactants comprising a hydrophobic radical anda negatively charged hydrophilic head group, amphoteric surfactants,which carry both a negative and a compensating positive charge, cationicsurfactants, which in addition to a hydrophobic radical have apositively charged hydrophilic group, and non-ionic surfactants, whichhave no charges but strong dipole moments and are strongly hydrated inaqueous solution.

Non-ionic surfactants contain, for example, a polyol group, apolyalkylene glycol ether group or a combination of polyol andpolyglycol ether group as the hydrophilic group. Such links include

-   -   Addition products of 2 to 50 mol ethylene oxide and/or 0 to 5        mol propylene oxide to linear and branched fatty alcohols with 6        to 30 C atoms, the fatty alcohol polyglycol ethers or the fatty        alcohol polypropylene glycol ethers or mixed fatty alcohol        polyethers,    -   Addition products of 2 to 50 mol ethylene oxide and/or 0 to 5        mol propylene oxide to linear and branched fatty acids with 6 to        30 C atoms, the fatty acid polyglycol ethers or the fatty acid        polypropylene glycol ethers or mixed fatty acid polyethers,    -   Addition products of 2 to 50 mol ethylene oxide and/or 0 to 5        mol propylene oxide to linear and branched alkylphenols having 8        to 15 C atoms in the alkyl group, the alkylphenol polyglycol        ethers or the alkylpolypropylene glycol ethers or mixed        alkylphenol polyethers,    -   with a methyl or C₂-C₆-alkyl radical end-group capped addition        products of 2 to 50 moles of ethylene oxide and/or 0 to 5 moles        of propylene oxide to linear and branched fatty alcohols with 8        to 30 C atoms, to fatty acids with 8 to 30 C atoms and to        alkylphenols with 8 to 15 C atoms in the alkyl group, such as        the grades available under the sales names Dehydol® LS, Dehydol®        LT (Cognis),    -   C₁₂-C₃₀ fatty acid mono- and diesters of addition products of 1        to 30 mol ethylene oxide to glycerol,    -   Addition products of 5 to 60 mol ethylene oxide to castor oil        and hardened castor oil,    -   Polyol fatty acid esters, such as the commercial product        Hydagen® HSP (Cognis) or Sovermol® grades (Cognis),    -   alkoxylated triglycerides,    -   alkoxylated fatty acid alkyl esters of the formula (Tnio-1)

R¹CO—(OCH₂CHR²)_(w)OR³  (Tnio-1)

in which R¹CO is a linear or branched, saturated and/or unsaturated acylradical having 6 to 22 carbon atoms, R² is hydrogen or methyl, R³ islinear or branched alkyl radicals having 1 to 4 carbon atoms and w isnumbers from 1 to 20,

-   -   amine oxides,    -   Hydroxy mixed ethers, as described for example in DE-OS        19738866,    -   Sorbitan fatty acid esters and addition products of ethylene        oxide to sorbitan fatty acid esters such as polysorbates,    -   Sugar fatty acid esters and addition products of ethylene oxide        to sugar fatty acid ester,    -   Addition products of ethylene oxide to fatty acid alkanolamides        and fatty amines,    -   Sugar tensides of the alkyl and alkenyl oligoglycoside type        according to formula (E4-II),

R⁴O-[G]_(p)  (Tnio-2)

in which R⁴ is an alkyl or alkenyl radical comprising 4 to 22 carbonatoms, G is a sugar residue comprising 5 or 6 carbon atoms and p is anumber of 1 to 10. They can be obtained by the relevant methods ofpreparative organic chemistry.

The alkyl and alkenyl oligoglycosides can be derived from aldoses orketoses with 5 or 6 carbon atoms, preferably glucose. The preferredalkyl and/or alkenyl oligoglycosides are thus alkyl and/or alkenyloligoglucosides. The index number p in the general formula (Tnio-2)indicates the degree of oligomerization (DP), i.e. the distribution ofmono- and oligoglycosides and stands for a number between 1 and 10.While p must always be an integer in the individual molecule and canassume the values p=1 to 6, the value p for a certain alkyloligoglycoside is an analytically determined arithmetical quantity,which usually represents a fractional number. Preferably alkyl and/oralkenyl oligoglycosides with an average degree of oligomerization p of1.1 to 3.0 are used. From an application technology point of view, thosealkyl and/or alkenyl oligoglycosides are preferred whose degree ofoligomerization is less than 1.7 and lies between 1.2 and 1.4.

The alkyl or alkenyl radical R⁴ can be derived from primary alcoholscomprising 4 to 11, preferably 8 to 10 carbon atoms. Typical examplesare butanol, caproic alcohol, caprylic alcohol, caprin alcohol andundecrylic alcohol as well as their technical mixtures, such as thoseobtained in the hydrogenation of technical fatty acid methyl esters orduring the hydrogenation of aldehydes from Roelen's oxo synthesis.Preferred are alkyl oligoglucosides with a chain length of C₈-C₁₀ (DP=1to 3), which are obtained as a preliminary step in the distillativeseparation of technical C₈-C₁₈ coconut-fatty alcohol and may becontaminated with less than 6 wt. % of C₁₂ alcohol, and alkyloligoglucosides based on technical C_(9/11) oxoalcohols (DP=1 to 3). Thealkyl or alkenyl radical R¹⁵ can also be derived from primary alcoholshaving 12 to 22, preferably 12 to 14 carbon atoms. Typical examples arelauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol,stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol,petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenylalcohol, erucyl alcohol, brassidyl alcohol and their technical mixtures,which can be obtained as described above.

Preferred are alkyl oligoglucosides based on hardened C12/14 coconutalcohol with a DP of 1 to 3.

-   -   Sugar surfactants of the fatty acid N-alkyl        polyhydroxyalkylamide type, a nonionic surfactant of formula        (Tnio-3)

R⁵CO—NR⁶—[Z]  (Tnio-3)

in which R⁵CO is an aliphatic acyl radical comprising 6 to 22 carbonatoms, R⁶ is hydrogen, an alkyl or hydroxyalkyl radical comprising 1 to4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radicalcomprising 3 to 12 carbon atoms and 3 to 10 hydroxyl groups. The fattyacid N-alkyl polyhydroxyalkylamides are known substances that canusually be obtained by reductive amination of a reducing sugar withammonia, an alkylamine or an alkanolamine and subsequent acylation witha fatty acid, a fatty acid alkyl ester or a fatty acid chloride. Thefatty acid N-alkyl polyhydroxyalkylamides are preferably derived fromreducing sugars with 5 or 6 carbon atoms, especially from glucose. Thepreferred fatty acid N-alkyl polyhydroxyalkylamides are therefore fattyacid N-alkylglucamides as represented by the formula (Tnio-4):

R⁷CO—(NR⁸)—CH₂—[CH(OH)]₄—CH₂OH  (Tnio-4)

Preferably, glucamides of the formula (Tnio-4) are used as fattyacid-N-alkyl polyhydroxyalkylamides, in which R⁸ represents hydrogen oran alkyl group and R⁷CO represents the acyl radical of caproic acid,caprylic acid, capric acid, Lauric acid, myristic acid, palmitic acid,palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid,petroselinic acid, linoleic acid, linolenic acid, arachidic acid,gadoleic acid, behenic acid or erucic acid or their technical mixtures.Particularly preferred are fatty acid N-alkyl glucamides of the formula(Tnio-4), which are obtained by reductive amination of glucose withmethylamine and subsequent acylation with lauric acid or C_(12/14)coconut fatty acid or a corresponding derivative. Furthermore,polyhydroxyalkylamides can also be derived from maltose and palatinose.

The sugar surfactants may preferably be present in the agent used ascontemplated herein in amounts of 0.1-20 wt. %, based on the totalagent. Amounts of 0.5-15 wt. % are preferred and amounts of 0.5-7.5 wt.% are particularly preferred.

Other typical examples of nonionic surfactants are fatty acid amidepolyglycol ethers, fatty amine polyglycol ethers, mixed ethers or mixedformals, protein hydrolysates (especially wheat-based vegetableproducts) and polysorbates.

The alkylene oxide addition products to saturated linear fatty alcoholsand fatty acids, each with 2 to 30 moles of ethylene oxide per mole offatty alcohol or fatty acid, and the sugar surfactants have proved to bepreferred nonionic surfactants. Preparations with excellent propertiesare also obtained if they contain fatty acid esters of ethoxylatedglycerol as non-ionic surfactants.

These connections are identified by the following parameters. The alkylradical R comprises 6 to 22 carbon atoms and can be either linear orbranched. Primary linear and in 2-position methyl-branched aliphaticradicals are preferred. Such alkyl radicals are for example 1-octyl,1-decyl, 1-lauryl, 1-myristyl, 1-cytyl and 1-stearyl. Especiallypreferred are 1-octyl, 1-decyl, 1-lauryl, 1-myristyl. When so-called“oxo-alcohols” are used as starting materials, compounds with an oddnumber of carbon atoms in the alkyl chain predominate.

The compounds with alkyl groups used as surfactants can each be uniformsubstances. However, it is usually preferable to start from native plantor animal raw materials in the production of these substances, so thatone obtains substance mixtures with different alkyl chain lengthsdepending on the respective raw material.

For surfactants which are products of the addition of ethylene and/orpropylene oxide to fatty alcohols or derivatives of these additionproducts, both products with a “normal” homologue distribution and thosewith a narrowed homologue distribution can be used. By “normal”homologue distribution we mean mixtures of homologues obtained in thereaction of fatty alcohol and alkylene oxide using alkali metals, alkalimetal hydroxides or alkali metal alcoholates as catalysts. Constrictedhomologue distributions are obtained, on the other hand, when, forexample, hydrotalcites, alkaline earth metal salts of ether carboxylicacids, alkaline earth metal oxides, hydroxides or alcoholates are usedas catalysts. The use of products with narrowed homologue distributionmay be preferred.

Particularly satisfactory results were obtained when the agent ascontemplated herein included (at least one ethoxylated fatty alcoholwith a degree of ethoxylation of 10 to 40.

In a further very particularly preferred embodiment, an agent ascontemplated herein comprises at least one nonionic surfactant which ispreferably selected from the nonionic surfactants of the formula (T-I)

-   -   wherein        Rb is a saturated or unsaturated, unbranched or branched C₈-C₂₄        alkyl group, preferably a saturated, unbranched C₁₆- to C₁₈        alkyl group, and        m an integer from 10 to 40, preferably an integer from 20 to 35,        and particularly preferably the number 30.

A particularly well-suited non-ionic surfactant of this type isceteareth-30. Ceteareth-30 is a mixture of cetyl alcohol and stearylalcohol, each ethoxylated with 30 units of ethylene oxide. The mixtureof cetyl alcohol and stearyl alcohol is called cetearyl alcohol.Ceteareth-30 has the CAS number 68439-49-6 and can be purchased, forexample, under the trade name Eumulgin B3 from BASF.

The nonionic surfactants, in particular the nonionic surfactants offormula (T-I), are preferably used in the appropriate amount ranges inagent (b). Thus, based on the total weight of agent (b), agent (b) maycontain one or more nonionic surfactants in a total amount of from about0.1 to about 20 wt. %, preferably from about 0.2 to about 10 wt. %, morepreferably from about 0.3 to about 5 wt. 00 and most preferably fromabout 0.4 to about 2.5 wt. %.

Water Content in Agent

The agent described above is a ready-to-use agent that can be applied tothe keratinous material. This ready-to-use agent preferably has a highwater content. It has been found that particularly suitable agents arethose comprising—based on the total weight of the agent—about 50.0 toabout 98.0 wt. %, preferably about 60.0 to about 90.0 wt. %, morepreferably about 70.0 to about 90.0 wt. % and most preferably about 75.0to about 90.0 wt. % of water.

In a further explicitly quite particularly preferred embodiment, anagent as contemplated herein comprises—based on the total weight of theagent—about 50.0 to about 98.0 wt. %, preferably about 60.0 to about90.0 wt. %, further preferably about 70.0 to about 90.0 wt. % and veryparticularly preferably about 75.0 to about 90.0 wt. % of water.

Other Optional Ingredients in the Agent

In addition to the ingredients (a1) to (a3) essential to the presentdisclosure already described, the agent may also contain furtheroptional ingredients.

For example, the agent may contain a film-forming polymer. Thefilm-forming polymer may be selected, for example, from the groupcomprising polyvinylpyrrolidone (PVP), vinylpyrrolidone/vinyl acetatecopolymers, vinylpyrrolidone/styrene copolymers,vinylpyrrolidone/ethylene copolymers, vinylpyrrolidone/propylenecopolymers, vinylpyrrolidone/vinylcaprolactam copolymers,vinylpyrrolidone/vinylformamide copolymers and/or vinylpyrrolidone/vinylalcohol copolymers, explicitly very particularly preferredpolyvinylpyrrolidone (PVP).

Further suitable film-forming polymers can be selected from the group ofcopolymers of acrylic acid, copolymers of methacrylic acid, homopolymersor copolymers of acrylic acid esters, homopolymers or copolymers ofmethacrylic acid esters, homopolymers or copolymers of acrylic acidamides, homopolymers or copolymers of methacrylic acid amides,copolymers of vinylpyrrolidone, copolymers of vinyl alcohol, copolymersof vinyl acetate, homopolymers or copolymers of ethylene, homopolymersor copolymers of propylene, homopolymers or copolymers of styrene,polyurethanes, polyesters and/or polyamides.

Film-forming polymers selected from the group of synthetic polymers,polymers obtainable by free-radical polymerization, or natural polymershave proven to be well suited.

Other particularly well-suited film-forming polymers can be selectedfrom the homopolymers or copolymers of olefins, such as cycloolefins,butadiene, isoprene or styrene, vinyl ethers, vinyl amides, the estersor amides of (meth)acrylic acid having at least one C₁-C₂₀ alkyl group,an aryl group or a C2-C10 hydroxyalkyl group.

Other film-forming polymers may be selected from the homo- or copolymersof isooctyl (meth)acrylate; isononyl (meth)acrylate; 2-ethylhexyl(meth)acrylate; lauryl (meth)acrylate); isopentyl (meth)acrylate;n-butyl (meth)acrylate); isobutyl (meth)acrylate; ethyl (meth)acrylate;methyl (meth)acrylate; tert-butyl (meth)acrylate; stearyl(meth)acrylate; hydroxyethyl (meth)acrylate; 2-hydroxypropyl(meth)acrylate; 3-hydroxypropyl (meth)acrylate; and/or mixtures thereof.

Further film-forming polymers may be selected from the homo- orcopolymers of (meth)acrylamide; N-alkyl-(meth)acrylamides, in those withC2-C18 alkyl groups, such as N-ethyl-acrylamide,N-tert-butyl-acrylamide, le N-octyl-crylamide;N-di(C1-C4)alkyl-(meth)acrylamide.

Other suitable anionic copolymers include copolymers of acrylic acid,methacrylic acid or their C₁-C₆ alkyl esters, as sold under the INCIdeclaration Acrylates Copolymers. A suitable commercial product is forexample Aculyn® 33 from Rohm & Haas. Copolymers of acrylic acid,methacrylic acid or their C₁-C₆ alkyl esters and the esters of anethylenically unsaturated acid and an alkoxylated fatty alcohol are alsopreferred. Suitable ethylenically unsaturated acids are especiallyacrylic acid, methacrylic acid and itaconic acid; suitable alkoxylatedfatty alcohols are especially steareth-20 or ceteth-20.

Polymers on the market include Aculyn® 22 (Acrylate/Steareth-20Me-thacrylate Copolymer), Aculyn® 28 (Acrylate/Beheneth-25 MethacrylateCopolymer), Structure 2001® (Acryla-tes/Steareth-20 ItaconateCopolymer), Structure 3001@ (Acrylate/Ceteth-20 Itaconate Copolymer),Structure Plus® (acrylate/aminoacrylate C10-30 alkyl PEG-20 itaconatecopolymer), Carbopol® 1342, 1382, Ultrez 20, Ultrez 21 (acrylate/C10-30alkyl acrylate crosspolymer), Synthalen W 2000® (acrylate/palmeth-25acrylate copolymer) or Soltex OPT (acrylate/C₁₂-22 alkyl methacrylatecopolymer) distributed by Rohme und Haas.

The homo- and copolymers of N-vinylpyrrolidone, vinylcaprolactam,vinyl-(C1-C6)alkyl-pyrrole, vinyl-oxazole, vinyl-thiazole,vinylpyrimidine, vinylimidazole can be named as suitable polymers basedon vinyl monomers.

Also suitable are the copolymersoctylacrylamide/acrylates/butylaminoethyl methacrylate copolymer, suchas those sold commercially under the trade names AMPHOMER® or LOVOCRYL®47 from NATIONAL STARCH, or the copolymers of acrylates/octylacrylamidessold under the trade names DERMACRYL® LT and DERMACRYL® 79 from NATIONALSTARCH.

Suitable olefin-based polymers include homopolymers and copolymers ofethylene, propylene, butene, isoprene and butadiene.

In another version, block copolymers can be used as film-forminghydrophobic polymers, which comprise at least one block of styrene orthe derivatives of styrene. These block copolymers can be copolymersthat contain one or more other blocks in addition to a styrene block,such as styrene/ethylene, styrene/ethylene/butylene, styrene/butylene,styrene/isoprene, styrene/butadiene. Such polymers are commerciallydistributed by BASF under the trade name “Luvitol HSB”.

If, in principle, both anionic and cationic and/or non-ionic polymerscan be used in the agent as contemplated herein, it has provedparticularly preferable not to use further ionic compounds or to usethem only in lesser amounts. In other words, a particularly strongimprovement in color intensity could be achieved when the agent was anon-ionic base and therefore included cationic and anionic polymerseither not at all or only in tiny amounts. For this reason, it has beenfound to be particularly preferable if the total content of all anionicpolymers included in the agent is below about 0.1 wt. %. Furthermore, ithas been found to be particularly preferred if the total content of allcationic polymers included in the agent is below about 0.1 wt. %. Theamount of catalytic or anionic polymer is related to the total weight ofthe agent.

In another very particularly preferred embodiment, an agent ascontemplated herein is wherein—in relation to the total weight of theagents

-   -   the total content of all anionic polymers included in the agent        is below about 0.1 wt. %, and    -   the total content of all cationic polymers included in the agent        is below about 0.1 wt. %.

In addition to the non-ionic surfactants described above, the agents canin principle also contain one or more charged surfactants. The termsurfactants refer to surface-active substances. A distinction is madebetween anionic surfactants comprising a hydrophobic radical and anegatively charged hydrophilic head group, amphoteric surfactants, whichcarry both a negative and a compensating positive charge, cationicsurfactants, which in addition to a hydrophobic radical have apositively charged hydrophilic group, and non-ionic surfactants, whichhave no charges but strong dipole moments and are strongly hydrated inaqueous solution.

Zwitterionic surfactants are those surface-active compounds which carryat least one quaternary ammonium group and at least one —COO⁽⁻⁾— or —SO₃⁽⁻⁾ group in the molecule. Particularly suitable zwitterionicsurfactants are the so-called betaines such as theN-alkyl-N,N-dimethylammonium-glycinate, for example thecocoalkyl-dimethylammoniumglycinate,N-acylaminopropyl-N,N-dimethylammoniumglycinate, for example,cocoacylaminopropyl dimethyl ammonium glycinate, and2-alkyl-3-carboxymethyl-3-hydroxyethyl imidazolines each having 8 to 18C atoms in the alkyl or acyl group, and cocoacylaminoethyl hydroxyethylcarboxymethyl glycinate. A preferred zwitterionic surfactant is thefatty acid amide derivative known under the INCI name cocamidopropylbetaine.

Ampholytic surfactants are surface-active compounds which, apart from aC₈-C₂₄ alkyl or acyl group, contain at least one free amino group and atleast one —COOH— or —SO₃H group in the molecule and can form internalsalts. Examples of suitable ampholytic surfactants are N-alkylglycines,N-alkylpropionic acids, N-alkylaminobutyric acids,N-alkyliminodipropionic acids,N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines,N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoaceticacids each with about 8 to 24 C atoms in the alkyl group. Typicalexamples of amphoteric or zwitterionic surfactants are alkylbetaines,alkylamidobetaines, amino-propionates, aminoglycinate,imidazoliniumbetaines and sulfobetaines.

Examples of ampholytic surfactants are N-cocosalkylaminopropionate,cocosacylaminoethylaminopropionate and C₁₂-C₁₈-acyl sarcosine.

In addition, the agents may also contain at least one cationicsurfactant. Cationic surfactants are surfactants, i.e., surface-activecompounds, each with one or more positive charges. Cationic surfactantscontain only positive charges. Usually, these surfactants are composedof a hydrophobic part and a hydrophilic head group, the hydrophobic partusually comprising a hydrocarbon backbone (e.g., comprising one or twolinear or branched alkyl chains) and the positive charge(s) being in thehydrophilic head group. Examples of cationic surfactants are

-   -   quaternary ammonium compounds which, as hydrophobic radicals,        may carry one or two alkyl chains with a chain length of 8 to 28        C atoms,    -   quaternary phosphonium salts substituted with one or more alkyl        chains with a chain length of 8 to 28 C atoms or    -   tertiary sulfonium salts.

Furthermore, the cationic charge can also be part of a heterocyclic ring(e.g., an imidazolium ring or a pyridinium ring) in the form of an oniumstructure. In addition to the functional unit carrying the cationiccharge, the cationic surfactant may also contain other unchargedfunctional groups, as is the case for example with esterquats. Thecationic surfactants are used in a total quantity of about 0.1 to about45 wt. %, preferably about 1 to about 30 wt. % and most preferably about1 to about 15 wt. %—based on the total weight of the respective agent.

Furthermore, the agent as contemplated herein may also contain at leastone anionic surfactant. Anionic surfactants are surface-active agentswith exclusively anionic charges (neutralized by a corresponding countercation). Examples of anionic surfactants are fatty acids, alkylsulphates, alkyl ether sulphates and ether carboxylic acids with 12 to20 C atoms in the alkyl group and up to 16 glycol ether groups in themolecule.

If, in principle, both anionic and cationic and/or non-ionic surfactantscan be used in the agent as contemplated herein, it has provedparticularly preferable not to use further ionic compounds or to usethem only in small quantities. In other words, a particularly strongimprovement in color intensity could be achieved when the agent was anon-ionic base and therefore included cationic and anionic surfactantseither not at all or only in tiny amounts. For this reason, it has beenfound to be particularly preferable if the total content of all anionicsurfactants included in the agent is below about 0.1 wt. %. Furthermore,it has been found to be particularly preferable if the total content ofall cationic surfactants included in the agent is below about 0.1 wt. %.The amount of catalytic or anionic surfactant is related to the totalweight of the product.

In another very particularly preferred embodiment, an agent ascontemplated herein is wherein—in relation to the total weight of theagents

-   -   the total content of all anionic surfactants included in the        agent is below about 0.1 wt. %, and    -   the total content of all cationic surfactants included in the        agent is below about 0.1 wt. %.

The agents may also contain other active ingredients, auxiliaries andadditives, such as solvents, structurants such as glucose, maleic acidand lactic acid, hair-conditioning compounds such as phospholipids, forexample lecithin and cephalins; perfume oils, dimethyl isosorbide andcyclodextrins; fiber structure-improving active ingredients, inparticular mono-, di- and oligosaccharides such as glucose, galactose,fructose, fructose and lactose; dyes for coloring the product;anti-dandruff active ingredients such as piroctone olamine, zinc omadineand climbazole; amino acids and oligopeptides; protein hydrolysates onan animal and/or vegetable basis, as well as in the form of their fattyacid condensation products or optionally anionically or cationicallymodified derivatives; vegetable oils; light stabilizers and UV blockers;active ingredients such as panthenol, pantothenic acid, pantolactone,allantoin, pyrrolidinonecarboxylic acids and their salts, and bisabolol;polyphenols, in particular hydroxycinnamic acids,6,7-dihydroxycoumarins, hydroxybenzoic acids, catechins, tannins,leucoanthocyanidins, anthocyanidins, flavanones, flavones and flavonols;Ceramides or pseudoceramides; vitamins, provitamins and vitaminprecursors; plant extracts; fats and waxes such as fatty alcohols,beeswax, montan wax and kerosene; Swelling and penetrating agents suchas glycerol, propylene glycol monoethyl ether, carbonates, hydrogencarbonates, guanidines, ureas and primary, secondary and tertiaryphosphates; opacifiers such as latex, styrene/PVP and styrene/acrylamidecopolymers; pearlescent agents such as ethylene glycol mono- anddistearate as well as PEG-3-distearate; and blowing agents such aspropane-butane mixtures, N₂0, dimethyl ether, CO2 and air.

The selection of these other substances will be made by the specialistaccording to the desired properties of the agents. Regarding otheroptional components and the quantities of these components used,explicit reference is made to the relevant manuals known to thespecialist. The additional active ingredients and auxiliary substancesare preferably used in the preparations as contemplated herein inquantities of about 0.0001 to about 25 wt. % each, in particular about0.0005 to about 15 wt. %, based on the total weight of the respectiveagent.

Agent pH Value

The pH value of the agent as contemplated herein is preferably adjustedto a neutral to alkaline pH. Most preferably, the agent has an alkalinepH value in the range of about 7.0 to about about 11.5 preferably fromabout 8.0 to about 11.0, and most preferably from about 8.5 to about10.5. Under basic conditions, the amino-functionalized silicone polymer(a1) can be dissolved or dispersed particularly well and withoutprotonation.

Within the scope of a further preferred embodiment, an agent ascontemplated herein has a pH of from about 7.0 to about 11.5 preferablyfrom about 8.0 to about 11.0, and particularly preferably from about 8.5to about 10.5.

To adjust the desired pH values, the agent may contain at least onealkalizing agent. The pH values for the purposes of the presentdisclosure are pH values measured at a temperature of 22° C.

As alkalizing agents, the agents may contain, for example, ammonia,alkanolamines and/or basic amino acids.

The alkanolamines which can be used in the agent of the presentdisclosure are preferably selected from primary amines having a C₂-C₆alkyl base which carries at least one hydroxyl group. Preferredalkanolamines are selected from the group formed by 2-aminoethan-1-ol(monoethanolamine), 3-aminopropan-1-ol, 4-aminobutan-1-ol,5-aminopentan-1-ol, 1-aminopropan-2-ol, 1-aminobutan-2-ol,1-aminopentan-2-ol, 1-aminopentan-3-ol, 1-aminopentan-4-ol,3-amino-2-methylpropan-1-ol, 1-amino-2-methylpropan-2-ol,3-aminopropan-1,2-diol, 2-amino-2-methylpropan-1,3-diol.

Alkanolamines particularly preferred as contemplated herein are selectedfrom 2-aminoethan-1-ol and/or 2-amino-2-methylpropan-1-ol. Aparticularly preferred embodiment is therefore wherein the agent ascontemplated herein comprises an alkanolamine selected from2-aminoethan-1-ol and/or 2-amino-2-methylpropan-1-ol as alkalizingagent.

For the purposes of the present disclosure, an amino acid is an organiccompound comprising at least one protonatable amino group and at leastone —COOH or —SO₃H group in its structure. Preferred amino acids areamino carboxylic acids, especially α-(alpha)-amino carboxylic acids andω-amino carboxylic acids, whereby α-amino carboxylic acids areparticularly preferred.

As contemplated herein, basic amino acids are those amino acids whichhave an isoelectric point pI of greater than 7.0.

Basic α-amino carboxylic acids contain at least one asymmetric carbonatom. In the context of the present disclosure, both enantiomers can beused equally as specific compounds or their mixtures, especially asracemates. However, it is particularly advantageous to use the naturallypreferred isomeric form, usually in L-configuration.

The basic amino acids are preferably selected from the group formed byarginine, lysine, ornithine and histidine, especially preferablyarginine and lysine. In another particularly preferred embodiment, anagent as contemplated herein is therefore wherein the alkalizing agentis a basic amino acid from the group arginine, lysine, ornithine and/orhistidine.

In addition, the product may contain other alkalizing agents, especiallyinorganic alkalizing agents. Inorganic alkalizing agents usable ascontemplated herein are preferably selected from the group formed bysodium hydroxide, potassium hydroxide, calcium hydroxide, bariumhydroxide, sodium phosphate, potassium phosphate, sodium silicate,sodium metasilicate, potassium silicate, sodium carbonate and potassiumcarbonate.

Particularly preferred alkalizing agents are ammonia, 2-aminoethan-1-ol(monoethanolamine), 3-aminopropan-1-ol, 4-aminobutan-1-ol,5-aminopentan-1-ol, 1-aminopropan-2-ol, 1-aminobutan-2-ol,1-aminopentan-2-ol, 1-aminopentan-3-ol, 1-aminopentan-4-ol,3-amino-2-methylpropan-1-ol, 1-Amino-2-methylpropan-2-ol,3-aminopropan-1,2-diol, 2-amino-2-methylpropan-1,3-diol, arginine,lysine, ornithine, histidine, sodium hydroxide, potassium hydroxide,calcium hydroxide, barium hydroxide, sodium phosphate, potassiumphosphate, sodium silicate, sodium metasilicate, potassium silicate,sodium carbonate and potassium carbonate.

In another very particularly preferred embodiment, a process ascontemplated herein is wherein the agent comprises at least onealkalizing agent selected from the group of ammonia, 2-aminoethan-1-ol(monoethanolamine), 3-aminopropan-1-ol, 4-aminobutan-1-ol,5-aminopentan-1-ol, 1-aminopropan-2-ol, 1-aminobutan-2-ol,1-aminopentan-2-ol, 1-aminopentan-3-ol, 1-aminopentan-4-ol,3-amino-2-methylpropan-1-ol, 1-amino-2-methylpropan-2-ol,3-aminopropane-1,2-diol, 2-amino-2-methylpropane-1,3-diol, arginine,lysine, omithine, histidine, sodium hydroxide, potassium hydroxide,calcium hydroxide, barium hydroxide, sodium phosphate, potassiumphosphate, sodium silicate, sodium metasilicate, potassium silicate,sodium carbonate and potassium carbonate.

Process for Dyeing Keratin Material

The agents described above can be excellently used in processes fordyeing keratinous material, especially human hair.

A second object of the present disclosure is therefore a method forcoloring keratinous material, in particular human hair, comprising thefollowing steps:

(1) Application of a coloring agent to the keratinous material, whereinthe coloring agent is an agent as disclosed in detail in the descriptionof the first subject matter of the present disclosure,(2) Exposure of the colorant to the keratinous material and(3) Rinse out the dye with water.

In step (1) of the process as contemplated herein, the agent of thefirst present disclosure is applied to the keratinous material, which ismost preferably human hair.

In step (2) of the process as contemplated herein, the agent is thenallowed to act on the keratinous material after its application. In thiscontext, different exposure times of, for example, about 30 seconds toabout 60 minutes are conceivable.

However, a major advantage of the dyeing system as contemplated hereinis that an intensive color result can be achieved even in short periodsafter short exposure times. For this reason, it is advantageous if theapplication mixture remains on the keratin material only forcomparatively short periods of time after its application, from about 30seconds to about 15 minutes, preferably from about 30 seconds to about10 minutes, and particularly preferably from about 1 to about 5 minutes.

In a further preferred embodiment, a method as contemplated herein is.exemplified by:

(2) Exposure of the colorant to the keratinous material for a periodranging from about 30 seconds to about 15 minutes, preferably from about30 seconds to about 10 minutes, and most preferably from about 1 toabout 5 minutes.

Finally, following the action of the application mixture on the keratinmaterial, it is rinsed with water in step (3) of the process.

Here, in one embodiment, the application mixture can be washed out withwater only, i.e., without the aid of an after-treatment agent or ashampoo. The use of a post-treatment agent or conditioner in step (6) isalso conceivable in principle.

However, to solve the task as contemplated herein and to increase theconvenience of use, it has proved particularly preferable to rinse theagent in step (3) exclusively with water without the aid of a furtherafter-treatment agent, shampoo or conditioner.

In a further preferred embodiment, a method as contemplated herein is.exemplified by:

(3) Rinse out the dye with water only.

Concerning the further preferred embodiments of the method ascontemplated herein, mutatis mutantis what has been said about theagents as contemplated herein applies.

Examples 1. Formulations

The following formulations were prepared (all data in wt. % unlessotherwise stated):

Colorants (V1) (E1) Cetyl alcohol 6.0 6.0 C12-C18 fatty alcohols (Loroltechn.) 6.0 6.0 Ceteareth-30 6.0 6.0 (Cetearyl alcohol, ethoxylated 30EO) Propylene carbonate — 6.0 Lavanya Zuni (organic pigment, Neelikon1.0 1.0 Red, 111P0200, CI 12490) Dow Corning 2-8566 (Siloxanes andSilicones, 2.5 2.5 3-[(2-Aminoethyl)amino]-2-methylpropyl Me,Di-Me-Siloxane″ Ammonia (25% aqueous solution)  0.20 0.20 Water ad 100ad 100

2. Application

After preparation, the respective agent (V1 and E1) was applied to hairstrands (Kerling, Euronatural hair white, liquor ratio: 1 g agent per ghair strand) applied. The agent was left to act for three minutes.Subsequently, the hair strand was thoroughly washed (1 minute) withwater, dried and then colorimetrically measured with a colorimeter fromDatacolor, type Spectraflash 450.

The dE value used to assess the color intensity is derived from theL*a*b* colorimetric values measured on the respective strand part asfollows:

dE=[(L_(i)-L₀)²+(a _(i)-a ₀)²+(b _(i)-b ₀)]^(1/2)

-   -   L₀, a₀ and b₀=Measured values of the comparative staining (V1)    -   L_(i), a_(i) ad b_(i)=Measured values of the dyeing as        contemplated herein (E)

The chroma of a coloration is calculated according to the formula:

C=√{square root over (a ² +b ²)},

where the larger the C-value, the higher the chromaticity of acoloration.

The L-value indicates the brightness of a coloration. The lower theL-value is, the darker and more intense the coloration is.

Agent L a b Chroma C dE for comparison Comparison (V1) 40.55 37.65 8.2238.54 Example (E1) 30.84 47.41 15.27 49.80 15.47

Darker, more intense colorations (lower L value) and higher chromaticity(higher C value) were measured with the agent of the present disclosure(E1).

While at least one exemplary embodiment has been presented in theforegoing detailed description, it should be appreciated that a vastnumber of variations exist. It should also be appreciated that theexemplary embodiment or exemplary embodiments are only examples, and arenot intended to limit the scope, applicability, or configuration of thevarious embodiments in any way. Rather, the foregoing detaileddescription will provide those skilled in the art with a convenient roadmap for implementing an exemplary embodiment as contemplated herein. Itbeing understood that various changes may be made in the function andarrangement of elements described in an exemplary embodiment withoutdeparting from the scope of the various embodiments as set forth in theappended claims.

1. An agent for dyeing keratinous material, the agent being acomposition comprising: (a1) at least one amino-functionalized siliconepolymer; (a2) at least one color-imparting compound; and (a3) at leastone organic carbonic acid ester.
 2. The agent of claim 1, wherein the atleast one amino-functionalized silicone polymer (a1) comprises at leastone secondary amino group.
 3. The agent of claim 1, wherein the at leastone amino-functionalized silicone polymer (a1) comprises at least onestructural unit of the formula (Si-Amino):

where ALK1 and ALK2 each independently represent a linear or branchedC₁-C₂₀ divalent alkylene group.
 4. The agent of claim 1, wherein the atleast one amino-functionalized silicone polymer (a1) comprises at leastone structural units of the formula (Si-I) and at least one structuralunit of the formula (Si-II):


5. The agent of claim 1, comprising the at least oneamino-functionalized silicone polymer (a1) in a total amount of fromabout 0.1 to about 8.0 wt. %, based on the total weight of thecomposition.
 6. The agent of claim 1, wherein the at least onecolor-imparting compound (a2) comprises a colorant compound selectedfrom the group of pigments, direct dyes, photochromic dyes, and-thermochromic dyes, and combinations thereof.
 7. The agent of claim 1,wherein the at least one color-imparting compound (a2) comprises aninorganic pigment selected from the group of colored metal oxides, metalhydroxides, metal oxide hydrates, silicates, metal sulfides, complexmetal cyanides, metal sulfates, bronze pigments colored mica- ormica-based pigments coated with at least one metal oxide and/or a metaloxychloride, and combinations thereof.
 8. The agent of claim 1, whereinthe at least one color-imparting compound (a2) comprises an organicpigments selected from the group of: carmine; quinacridone;phthalocyanine; sorghum; blue pigments with the color index numbers CI42090, CI 69800, CI 69825, CI 73000, CI 74100, or CI 74160; yellowpigments with the color index numbers CI 11680, CI 11710, CI 15985, CI19140, CI 20040, CI 21100, CI 21108, CI 47000, or CI 47005; greenpigments with Color Index numbers CI 61565, CI 61570, or CI 74260;orange pigments with Color Index numbers CI 11725, CI 15510, CI 45370,or CI 71105; red pigments with Color Index numbers CI 12085, CI 12120,CI 12370, CI 12420, CI 12490, CI 14700, CI 15525, CI 15580, CI 15620, CI15630, CI 15800, CI 15850, CI 15865, CI 15880, CI 17200, CI 26100, CI45380, CI 45410, CI 58000, CI 73360, CI 73915 or CI 75470; andcombinations thereof.
 9. The agent of claim 1, comprising the at leastone color-imparting compound (a2) in a total amount of from about 0.01to about 10.0 wt %, based on the total weight of the composition. 10.The agent of claim 1, wherein the at least one organic carbonic acidester (a3) comprises the general formula (KSE-I):

where: (i) R₁ and R₂-together with the two oxygen atoms to which theyare attached and together with the carbonyl group form a 5-membered,6-membered or 7-membered ring, which ring is optionally substituted witha C₁-C₁₂ alkyl group, a hydroxy-C₁-C₆ alkyl group, a hydroxy group or aC₁-C₆ alkoxy group; or (ii) R₁ and R₂ each independently represent aC₁-C₁₂ alkyl group, a hydroxy-C₁-C₁₂ alkyl group, or an optionallysubstituted aryl group.
 11. The agent of claim 1, wherein the at leastone organic carbonic acid ester (a3) comprises at least one cyclicorganic carbonic acid ester selected from the group of substituted andunsubstituted 1,3-dioxolan-2-ones.
 12. The agent of claim 1, wherein theat least one organic carbonic acid ester (a3) comprises at least oneorganic carbonic acid ester of the general formula (KSE-II):

where R₃ is a methyl group, an ethyl group, an n-propyl group, aniso-propyl group, a hydroxymethyl group, or a hydroxyethyl group. 13.The agent of claim 1, wherein the at least one organic carbonic acidester (a3) comprises at least one selected from the group of4-methyl-1,3-dioxolane, 4-hydroxymethyl-1-3-dioxolane, di(n-octylcarbonate), di(n-hexyl carbonate), di(n-propyl carbonate), dimethylcarbonate, diethyl carbonate, and diphenyl carbonate.
 14. The agent ofclaim 1, comprising the at least one organic carbonic acid ester (a3) ina total amount of from about 0.1 to about 20.0 wt. %, based on the totalweight of the composition.
 15. The agent of claim 1, wherein thecomposition further comprises a fat constituent (a4) comprising at leastone C₁₂-C₂₄ fatty alcohol selected from the group of dodecan-1-ol,tetradecan-1-ol-, hexadecan-1-ol-, octadecan-1-ol-, arachyl alcohol,heneicosyl alcohol, behenyl alcohol, (9Z)octadec-9-en-1-ol-,(9E)-octadec-9-en-1-ol (9Z,12Z)octadeca-9,12-dien-1-ol,(9Z,12Z,15Z)-octadeca-9,12,15-trien-1-ol, (9Z)-eicos-9-en-1-ol,(5Z,8Z,11Z,14Z)eicosa-5,8,11,14-tetraen-1-ol, -(13Z)docos-13-en-1-ol,(13-E-)docosen-1-ol, 2-octyl-dodecanol, 2-hexyl-dodecanol,2-butyl-dodecanol, and combinations thereof.
 16. The agent of claim 1,wherein the composition further comprises at least one nonionicsurfactant of the formula (T-I):

where Rb is a saturated or unsaturated, unbranched or branched C₈-C₂₄alkyl group; and m is an integer of from 10 to
 40. 17. The agent ofclaim 1, wherein the composition further comprises water and has a pH offrom about 7.0 to about 11.5.
 18. A process for dyeing keratinousmaterial, comprising: (1) applying a colorant to the keratinousmaterial, the colorant comprising the agent of claim 1; (2) exposing thekeratinous material to the agent for an exposure time sufficient for thecolor-imparting compound to act on the keratinous material; and (3)rinsing out the keratinous material with water to remove the coloranttherefrom.
 19. The process of claim 18, wherein the exposure time is inthe range of from about 30 seconds to about 15 minutes.
 20. The processof claim 18, wherein the agent composition: (i) comprises the one ormore amino-functionalized silicone polymers (a1) in a total amount offrom about 0.1 to about 8.0 wt. %, the one or more color-impartingcompounds (a2) in a total amount of from about 0.01 to about 10.0 wt. %,and the one or more organic carbonic acid esters (a3) in a total amountof from about 0.1 to about 20.0 wt. %, each based on the based on thetotal weight of the composition; (ii) further comprises a fatconstituent (a4) comprising at least one C₁₂-C₂₄ fatty alcohol; (iii)further comprises at least one nonionic surfactant; (iv) furthercomprises water; (v) has a pH of from about 7.0 to about 11.5; or (vi)any combination of (i)-(v).